WO2011087101A1 - Photocurable resin composition and light-emitting element sealant - Google Patents
Photocurable resin composition and light-emitting element sealant Download PDFInfo
- Publication number
- WO2011087101A1 WO2011087101A1 PCT/JP2011/050578 JP2011050578W WO2011087101A1 WO 2011087101 A1 WO2011087101 A1 WO 2011087101A1 JP 2011050578 W JP2011050578 W JP 2011050578W WO 2011087101 A1 WO2011087101 A1 WO 2011087101A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- photocurable resin
- butadiene rubber
- light
- group
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 44
- 239000000565 sealant Substances 0.000 title abstract 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 42
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 23
- -1 acyl phosphine oxide Chemical compound 0.000 claims abstract description 17
- 239000003566 sealing material Substances 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229920006295 polythiol Polymers 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 238000002834 transmittance Methods 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 235000006708 antioxidants Nutrition 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910002012 Aerosil® Inorganic materials 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- FEODVXCWZVOEIR-UHFFFAOYSA-N (2,4-ditert-butylphenyl) octyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C FEODVXCWZVOEIR-UHFFFAOYSA-N 0.000 description 1
- UTMRXNXUXKXVNK-UHFFFAOYSA-N (8-methyl-1-phenylnonyl) dihydrogen phosphite Chemical compound CC(C)CCCCCCC(OP(O)O)C1=CC=CC=C1 UTMRXNXUXKXVNK-UHFFFAOYSA-N 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N (R)-alpha-Tocopherol Natural products OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- FZLHAQMQWDDWFI-UHFFFAOYSA-N 2-[2-(oxolan-2-yl)propan-2-yl]oxolane Chemical compound C1CCOC1C(C)(C)C1CCCO1 FZLHAQMQWDDWFI-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
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- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
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- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- NFMHSPWHNQRFNR-UHFFFAOYSA-N hyponitrous acid Chemical class ON=NO NFMHSPWHNQRFNR-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VGMQZCPHUDXGFR-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].[Li].C1=CC=CC2=CC=CC=C21 VGMQZCPHUDXGFR-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- FEKRFYZGYUTGRY-UHFFFAOYSA-N n'-ethylmethanediimine Chemical compound CCN=C=N FEKRFYZGYUTGRY-UHFFFAOYSA-N 0.000 description 1
- CMESPBFFDMPSIY-UHFFFAOYSA-N n,n'-diphenylmethanediimine Chemical compound C1=CC=CC=C1N=C=NC1=CC=CC=C1 CMESPBFFDMPSIY-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- ACLZYRNSDLQOIA-UHFFFAOYSA-N o-tolylthiourea Chemical compound CC1=CC=CC=C1NC(N)=S ACLZYRNSDLQOIA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical group CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- ZKDDJTYSFCWVGS-UHFFFAOYSA-M sodium;diethoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Na+].CCOP([S-])(=S)OCC ZKDDJTYSFCWVGS-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- AOBORMOPSGHCAX-DGHZZKTQSA-N tocofersolan Chemical compound OCCOC(=O)CCC(=O)OC1=C(C)C(C)=C2O[C@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C AOBORMOPSGHCAX-DGHZZKTQSA-N 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5397—Phosphine oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
Definitions
- the present invention relates to a photocurable resin composition and a light emitting device sealing material using the photocurable resin composition.
- Sealing materials for electronic displays such as organic electroluminescent elements and inorganic electroluminescent elements, backlights for electronic devices such as mobile phones, digital video cameras, PDAs such as LEDs, display units such as large displays, road indicators,
- a sealing material for general lighting, etc. it is required to have an effect of protecting light from external impacts, dust, moisture, etc., and at the same time improving the light extraction efficiency.
- thermosetting epoxy resins see Patent Document 1
- thermosetting silicone resins see Patent Document 2
- ultraviolet curable urethane resins see Patent Document 3
- thermosetting epoxy resin described in Patent Document 1 When the thermosetting epoxy resin described in Patent Document 1 is used as a sealing material for a light-emitting element, there is a problem that the heat resistance is insufficient and it cannot withstand long-term use.
- thermosetting silicone resin described in Patent Document 2 When the thermosetting silicone resin described in Patent Document 2 is used, there is a problem that the adhesiveness and flexibility are insufficient, and thus convenience is lacking. Further, the thermosetting resin itself has a problem that the time required for curing is long and the productivity is poor.
- the ultraviolet curable urethane resin described in Patent Document 3 when the ultraviolet curable urethane resin described in Patent Document 3 is used as a sealing material for a light-emitting element, the time required for curing is short and the productivity is increased, but the heat resistance is not sufficient, and discoloration due to heat is caused. This may cause problems such as affecting the luminance.
- an object of the present invention is to provide a light-curable resin composition that can provide a light-emitting element sealing material that can improve productivity by shortening the time required for curing, and has excellent heat resistance and light transmittance, and the light. It is providing the light emitting element sealing material using a curable resin composition.
- the inventors of the present invention require curing for a photocurable resin composition containing a terminal-modified hydrogenated styrene butadiene rubber and a specific photopolymerization initiator in a specific ratio. It has been found that a light-emitting element sealing material can be provided that can improve productivity with a short time, and that is excellent in both heat resistance and light transmittance.
- the present invention relates to the following [1] to [5].
- [1] Contains 100 parts by mass of (A) terminal-modified hydrogenated styrene butadiene rubber and (B) 0.1-13 parts by mass of an ⁇ -hydroxyalkylphenone photopolymerization initiator and / or an acylphosphine oxide photopolymerization initiator A photocurable resin composition.
- [2] The photocurable resin composition according to the above [1], wherein the terminal-modified hydrogenated styrene butadiene rubber of the component (A) is a hydrogenated styrene butadiene rubber having (meth) acryloyloxy groups at both ends of the molecule. object.
- the photocurable resin composition of the present invention requires a short time for curing, the productivity is enhanced and a light emitting device sealing material having excellent heat resistance and light transmittance can be provided.
- the photocurable resin composition of the present invention comprises (A) 100 parts by mass of a terminal-modified hydrogenated styrene butadiene rubber and (B) an ⁇ -hydroxyalkylphenone photopolymerization initiator and / or an acylphosphine oxide photopolymerization initiator 0. 1 to 13 parts by mass are contained.
- the terminal-modified hydrogenated styrene butadiene rubber as the component (A) is preferably one in which both ends of the hydrogenated styrene butadiene rubber are substituted with a photocurable functional group such as a (meth) acryloyl group.
- the method for producing the terminal-modified hydrogenated styrene butadiene rubber is not particularly limited.
- a hydroxyl group is introduced into the molecular terminal by reacting an unmodified hydrogenated styrene butadiene rubber with ethylene oxide or propylene oxide.
- a method of reacting with a compound having a photocurable functional group such as a (meth) acryloyl group is preferred.
- reaction with the compound having a photocurable functional group examples include a urethanation reaction with a hydrogenated styrene butadiene rubber having a hydroxyl group introduced at the molecular terminal and 2- (meth) acryloyloxyethyl isocyanate; a hydroxyl group at the molecular terminal Transesterification reaction of hydrogenated styrene butadiene rubber with methyl introduced and lower alkyl (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, etc .;
- a terminal-modified hydrogenated styrene butadiene rubber can be obtained by a reaction of a prepolymer obtained by reacting a styrene butadiene rubber with an isocyanate compound and 2-hydroxyethyl acrylate.
- the terminal-modified hydrogenated styrene butadiene rubber is preferably
- the unmodified hydrogenated styrene butadiene rubber can be obtained by hydrogenating a styrene butadiene rubber or a styrene butadiene rubber having a hydroxyl group introduced at the molecular end.
- the raw material styrene-butadiene rubber can be obtained by copolymerization of styrene and butadiene.
- a known dilithium compound such as naphthalene dilithium and dilithiohexylbenzene and a solvent inert to the reaction.
- 10 Examples include a method of copolymerizing styrene and 1,3-butadiene at -80 ° C.
- a heterogeneous catalyst in which styrene butadiene rubber is supported on a carrier such as Raney nickel or Pt, Pd, Ru, Rh, Ni on a support such as carbon, alumina, diatomaceous earth Ziegler-type catalyst consisting of a combination of organometallic compounds consisting of Group 8-10 metals such as nickel and cobalt and organoaluminum compounds such as triethylaluminum and triisobutylaluminum or organolithium compounds: transitions such as titanium, zirconium and hafnium 50 in the presence of a known hydrogenation catalyst such as a metallocene catalyst comprising a combination of a metal bis (
- the conjugated diene portion can be hydrogenated.
- the hydrogenation rate of the styrene butadiene rubber or the styrene butadiene rubber having a hydroxyl group introduced at the molecular end is not particularly limited, but is preferably 80 to 100%, more preferably 90 to 100% from the viewpoint of heat resistance.
- the weight average molecular weight of the terminal-modified hydrogenated styrene butadiene rubber is preferably 5,000 to 40,000, more preferably 10,000 to 30,000, and still more preferably 15,000 to 20,000.
- a weight average molecular weight is the value calculated
- the molecular weight distribution (Mw / Mn) is preferably 3 or less, more preferably 2 or less, and still more preferably 1.2 or less.
- the weight average molecular weight of the terminal-modified hydrogenated styrene butadiene rubber is within this range, the viscosity of the terminal-modified hydrogenated styrene butadiene rubber does not become too high, and the handleability is good. Moreover, if the molecular weight distribution is 3 or less, it is easy to obtain reproducibility in mass production, and it becomes easy to obtain a copolymer having the same molecular weight.
- the content of the structural unit derived from styrene in the terminal-modified hydrogenated styrene-butadiene rubber (hereinafter referred to as styrene content) is not particularly limited, but is preferably 10 to 40% by mass, more preferably based on the total structural unit. Is 10 to 30% by mass.
- the photocurable resin composition of the present invention contains at least one of an ⁇ -hydroxyalkylphenone photopolymerization initiator and an acylphosphine oxide photopolymerization initiator as component (B).
- an ⁇ -hydroxyalkylphenone photopolymerization initiator those represented by the following general formula (I) are preferable.
- R 1 , R 1 ′ , R 2 and R 2 ′ each independently represent an alkyl group having 1 to 5 carbon atoms, or R 1 and R 2 , R 1 ′ and R 2 ′. Together represent an alkylene group having 1 to 5 carbon atoms. R 1 and R 1 ′ , R 2 and R 2 ′ may be the same or different.
- W, Z and Z ′ each independently represents an alkylene group having 1 to 5 carbon atoms. Z and Z ′ may be the same or different.
- m is 0 or 1.
- n1 and n2 each independently represents 0 or 1.
- Examples of the alkyl group having 1 to 5 carbon atoms independently represented by R 1 , R 1 ′ , R 2 and R 2 ′ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group and the like. Can be mentioned. Among these, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
- Examples of the alkylene group having 1 to 5 carbon atoms represented by R 1 and R 2 and R 1 ′ and R 2 ′ together include a methylene group, an ethylene group, a tetramethylene group, and a pentamethylene group.
- a pentamethylene group is preferable.
- the alkylene group having 1 to 5 carbon atoms each independently represented by W, Z and Z ′ include a methylene group, an ethylene group and a trimethylene group.
- W is preferably a methylene group.
- Z and Z ′ both are preferably a methylene group or an ethylene group, more preferably an ethylene group.
- Preferred specific examples of the ⁇ -hydroxyalkylphenone photopolymerization initiator represented by the general formula (I) are shown below, but are not particularly limited thereto.
- acylphosphine oxide photopolymerization initiator for example, those represented by the following general formula (II) or (III) are preferable.
- R 3 , R 3 ′ and R 3 ′′ each independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
- R 4 represents an alkyl group having 1 to 15 carbon atoms.
- p1, p2 and p3 each independently represents an integer of 0 to 3.
- q represents 0 or 1;
- Examples of the alkyl group having 1 to 5 carbon atoms independently represented by R 3 , R 3 ′, and R 3 ′′ include a methyl group, an ethyl group, and various propyl groups (“various” means linear and all branched chains). The same applies hereinafter), and various butyl groups. Among these, a methyl group is preferable.
- Examples of the alkoxy group having 1 to 5 carbon atoms independently represented by R 3 , R 3 ′ and R 3 ′′ include a methoxy group and an ethoxy group. Among these, a methoxy group is preferable.
- Examples of the alkyl group having 1 to 15 carbon atoms represented by R 4 include a methyl group, an ethyl group, various propyl groups, various butyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, and the like.
- an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 4 to 10 carbon atoms is more preferable, and an alkyl group having 5 to 8 carbon atoms is more preferable.
- p1 is preferably 3.
- p2 is preferably 0 when q is 0, and preferably 3 when q is 1.
- p3 is preferably 0.
- both p1 and p2 are preferably 2.
- Preferable specific examples of the acylphosphine oxide photopolymerization initiator represented by the general formula (II) are shown below, but are not particularly limited thereto.
- Other photopolymerization initiators such as benzyl dimethyl ketal, ⁇ -aminoalkylphenone photopolymerization initiators, oxyphenylacetic acid ester photopolymerization initiators, and the like are used for cured products obtained from photocurable resin compositions. It was found that the light transmittance was poor and it was not useful as a light emitting device sealing material.
- the photocurable resin composition of the present invention may contain these other photopolymerization initiators as long as the effects of the present invention are not lost.
- the content thereof is preferably 5 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of component (A), from the viewpoint of light transmittance of the light emitting device sealing material. Is 3 parts by mass or less, more preferably 1 part by mass or less.
- the photocurable resin composition of the present invention may further contain a reactive diluent.
- a reactive diluent a liquid photopolymerizable monovinyl monomer can be used.
- the reactive diluent reduces the viscosity of the photocurable resin composition and facilitates application, and can be polymerized when the photocurable resin composition is photocured.
- Specific examples of the reactive diluent include vinyl esters such as vinyl acetate, (meth) acrylic monomers, N-vinyl monomers, polythiol compounds, and the like.
- Examples of the (meth) acrylic monomer include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, n-octadecyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl ( Examples include (meth) acrylates and esters of (meth) acrylic acid and polyhydric alcohols.
- N-vinyl monomer examples include N, N-dimethylacrylamide, N-vinylpyrrolidone, N-vinylcaprolactam and the like.
- the polythiol compound is not particularly limited as long as it has 2 to 6 mercapto groups in the molecule.
- aliphatic polythiols such as alkanedithiol having about 2 to 20 carbon atoms; aromatics such as xylylenedithiol Polythiols; polythiols obtained by substituting halogen atoms of halohydrin adducts of alcohols with mercapto groups; polythiols comprising hydrogen sulfide reaction products of polyepoxide compounds; polyhydric alcohols having 2 to 6 hydroxyl groups in the molecule And polythiols formed by esterification with thioglycolic acid, ⁇ -mercaptopropionic acid, or ⁇ -mercaptobutanoic acid.
- the component (C) is contained in the photocurable resin composition, the content thereof is preferably 5 to 70% by mass, more preferably 10 to 50% by mass with respect to the photocurable resin composition.
- the photocurable resin composition of the present invention may further contain various additives.
- additives include photosensitizers, inorganic fillers, thickeners, ultraviolet absorbers, antioxidants (anti-aging agents), N, N′-diphenylcarbodiimide, N, N′-ethylcarbodiimide, and the like. Examples thereof include carbodiimide compounds.
- photosensitizers include amine compounds such as aliphatic amines and aromatic amines; ureas such as o-tolylthiourea; sodium diethyldithiophosphate, s-benzylisothiouronium-p-toluenesulfonate, and the like. Sulfur compounds; Nitriles such as N, N-disubstituted-p-aminobenzonitrile compounds; Phosphorus compounds such as tri-n-butylphosphine; Other nitrogen compounds such as N-nitrosohydroxylamine derivatives .
- thickener By adding a thickener to the photocurable resin composition, thickening and thixotropic properties are imparted, and moldability can be improved.
- the thickener include inorganic fillers and organic thickeners.
- the inorganic filler include surface-treated fine silica of wet silica and dry silica, and natural minerals such as organic bentonite.
- silica fine powder pulverized by a dry method for example, “Aerosil 300” (manufactured by Nippon Aerosil Co., Ltd.)]
- fine powder obtained by modifying this silica fine powder with trimethyldisilazane for example, “Aerosil” RX300 "(manufactured by Nippon Aerosil Co., Ltd.) and the like
- fine powder obtained by modifying the silica fine powder with polydimethylsiloxane for example
- Aerosil RY300 “(manufactured by Nippon Aerosil Co., Ltd.)
- the average particle diameter of the inorganic filler is preferably 5 to 50 ⁇ m, more preferably 5 to 12 ⁇ m, from the viewpoints of thickening and transparency.
- the organic thickener include amide wax, hydrogenated castor oil, or a mixture thereof.
- hydrogenated castor oil which is a hydrogenated product of castor oil (non-drying oil whose main component is ricinoleic acid)
- ADVITOLOL 100 manufactured by Zudchemy Catalyst Co., Ltd.
- Disaron (registered trademark) 305 (Made by Enomoto Kasei Co., Ltd.) and the like
- higher amide waxes which are compounds obtained by substituting hydrogen of ammonia with an acyl group
- Disaron (registered trademark) 6500 made by Enomoto Kasei Co., Ltd.
- UV absorber- Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, benzoate compounds, triazine compounds, hydroxylamine compounds, and the like.
- Antioxidant- Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.
- phenolic antioxidants examples include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl- ⁇ - (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4- Hydroxy-5-tert-butylphenylbutane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis -[Methylene-3- (3 ′, 5′-d
- sulfur-based antioxidants include dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, and phosphorus-based oxidation
- the inhibitor include triphenyl phosphite, diphenylisodecyl phosphite, phenylisodecyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, Examples include -methylenebis (4,6-di-t-butylphenyl) octyl phosphite.
- the total content is not particularly limited as long as the effect of the present invention is not lost, but with respect to 100 parts by mass of component (A). Usually, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.
- the photocurable resin composition of the present invention can be obtained by mixing the component (A) and the component (B) and, if necessary, the component (C) and the component (D). Since the photocurable resin composition of the present invention is excellent in heat resistance and light transmittance, it is particularly useful as a light emitting device sealing material.
- the light emitting diode (LED) represented by the organic electroluminescent element and the inorganic electroluminescent element, and the laser diode (LD) used as a light source of communication and an optical disk are mentioned.
- a light emitting device sealing material By using the photocurable resin composition of the present invention, a light emitting device sealing material can be produced. Specifically, for example, a photocurable resin composition obtained by mixing well in a mixer such as a planetary mixer is applied to a portion to be sealed of the light emitting element, cured by irradiation with active energy rays, It becomes a light emitting element sealing material.
- the active energy rays include particle rays, electromagnetic waves, and combinations thereof.
- the particle beam include an electron beam (EB) and an ⁇ ray
- examples of the electromagnetic wave include an ultraviolet ray (UV), a visible ray, an infrared ray, a ⁇ ray and an X ray.
- ultraviolet rays As active energy rays.
- the ultraviolet light source include a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a microwave excimer lamp.
- the active energy ray is preferably irradiated in an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere in which the oxygen concentration is lowered, but can be sufficiently cured even in a normal air atmosphere.
- the irradiation temperature is usually preferably 10 to 200 ° C.
- the irradiation time is usually preferably 10 seconds to 60 minutes.
- the integrated light quantity is usually preferably 1,000 to 20,000 mJ / cm 2 .
- the mixture was heated to 50 ° C., polymerized for 1.5 hours, 108.0 ml of a 1 mol / L ethylene oxide cyclohexane solution was added, and the mixture was further stirred for 2 hours, and then 50 ml of isopropyl alcohol was added.
- a hexane solution of the obtained copolymer is precipitated in isopropyl alcohol and sufficiently dried to give a styrene butadiene rubber having a hydroxyl group at the molecular end (styrene content: 20% by mass, weight average molecular weight 18,000, molecular weight distribution). 1.15) was obtained.
- the catalyst residue was extracted and separated with 3 mol / m 3 hydrochloric acid, and further centrifuged to separate the catalyst residue by sedimentation. Then, a hydrogenated styrene butadiene rubber having a hydroxyl group at the molecular end is precipitated in isopropyl alcohol and further sufficiently dried to obtain a hydrogenated styrene butadiene rubber having a hydroxyl group at the molecular end (styrene content 20 mass%, weight average molecular weight). 16,500, hydrogenation rate: 98%, molecular weight distribution 1.1) was obtained.
- Examples 1 to 4 Each component was mixed with the planetary mixer by the compounding quantity (unit: mass part) shown in Table 1 and Table 2, and the photocurable resin composition was obtained.
- the obtained photocurable resin composition was formed into a film having a thickness of 1 mm or 2 mm after curing, and irradiated with active energy rays to obtain a cured product as a test piece.
- a light source for active energy rays a metal halide lamp (device name “SE-1500M”, manufactured by Sen Engineering Co., Ltd.) was used, and an ultraviolet irradiation device (device name “UV1501BA-LT”, manufactured by Sen Engineering Co., Ltd.) was used.
- the cured product obtained from the photocurable resin composition of the present invention has a higher light transmittance than the cured product obtained in the comparative example, and even when a test piece having a thickness of 2 mm is used. It can be seen that the light transmittance exceeds 80%, which is useful as a light emitting device sealing material.
- Comparative Example 6 when the content of the component (B) was increased, the component (B) was not completely dissolved, and it is considered that the light transmittance was greatly reduced.
- Example 1 Measurement of heat resistance
- the transmittance of light having a wavelength of 400 nm after being held for 100 hours or 1000 hours was measured by the same method as described above, and the relative value when the initial value was taken as 100 was determined, and the heat resistance of the obtained cured product was evaluated.
- the results are shown in Table 2. In addition, it shows that it is excellent in heat resistance, when the reduction
- Example 1 Measurement of heat resistance
- urethane acrylate (“Light Tack PUA-KH32M", manufactured by Kyoeisha Chemical Co., Ltd.) is used instead of the terminal-modified hydrogenated styrene butadiene rubber of component (A).
- a cured product (thickness 2 mm) was obtained in the same manner except that it was, and in the same manner as in Test Example 1, the heat resistance of the obtained cured product was evaluated. The results are shown in Table 2.
- the cured product obtained by curing the photocurable resin composition of the present invention has excellent heat resistance and is useful as a light emitting device sealing material.
- the photocurable resin composition of the present invention is excellent in heat resistance and light transmittance, it is used as a sealing material for electronic displays such as organic electroluminescent elements and inorganic electroluminescent elements, mobile phones using LEDs, and digital video. It can be used as a backlight for electronic devices such as cameras and PDAs, a display unit such as a large display, a road indicator, and a light emitting element sealing material for general lighting.
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Abstract
Disclosed is a photocurable resin composition that cures quickly, thereby improving productivity, and can provide a light-emitting element sealant that is highly heat-resistant and optically transparent. Also disclosed is a light-emitting element sealant using said photocurable resin composition. The photocurable resin composition contains: (A) 100 mass parts of an end-modified hydrogenated styrene-butadiene rubber; and (B) 0.1 to 13 mass parts of an α-hydroxyalkyl-phenol photopolymerization initiator and/or an acyl phosphine oxide photopolymerization initiator.
Description
本発明は、光硬化性樹脂組成物及び該光硬化性樹脂組成物を用いた発光素子封止材に関する。
The present invention relates to a photocurable resin composition and a light emitting device sealing material using the photocurable resin composition.
有機エレクトロルミネッセンス素子及び無機エレクトロルミネッセンス素子等の電子ディスプレイの封止材や、ＬＥＤが用いられる携帯電話、デジタルビデオカメラ、ＰＤＡ等の電子機器のバックライト、大型ディスプレイ、道路表示器等の表示部、及び一般照明の封止材等としては、外部からの衝撃、埃及び水分等から保護すると同時に、光取り出し効率を向上させる等の効果を有することが求められ、その材料の開発が進められている。
従来は、シール材として、熱硬化性エポキシ樹脂（特許文献１参照）、熱硬化性シリコーン樹脂（特許文献２参照）及び紫外線硬化性ウレタン樹脂（特許文献３参照）が用いられており、これらを発光素子の封止材として利用することが検討されてきた。 Sealing materials for electronic displays such as organic electroluminescent elements and inorganic electroluminescent elements, backlights for electronic devices such as mobile phones, digital video cameras, PDAs such as LEDs, display units such as large displays, road indicators, As a sealing material for general lighting, etc., it is required to have an effect of protecting light from external impacts, dust, moisture, etc., and at the same time improving the light extraction efficiency. .
Conventionally, thermosetting epoxy resins (see Patent Document 1), thermosetting silicone resins (see Patent Document 2), and ultraviolet curable urethane resins (see Patent Document 3) are used as sealing materials. Utilization as a sealing material of a light emitting element has been studied.
従来は、シール材として、熱硬化性エポキシ樹脂（特許文献１参照）、熱硬化性シリコーン樹脂（特許文献２参照）及び紫外線硬化性ウレタン樹脂（特許文献３参照）が用いられており、これらを発光素子の封止材として利用することが検討されてきた。 Sealing materials for electronic displays such as organic electroluminescent elements and inorganic electroluminescent elements, backlights for electronic devices such as mobile phones, digital video cameras, PDAs such as LEDs, display units such as large displays, road indicators, As a sealing material for general lighting, etc., it is required to have an effect of protecting light from external impacts, dust, moisture, etc., and at the same time improving the light extraction efficiency. .
Conventionally, thermosetting epoxy resins (see Patent Document 1), thermosetting silicone resins (see Patent Document 2), and ultraviolet curable urethane resins (see Patent Document 3) are used as sealing materials. Utilization as a sealing material of a light emitting element has been studied.
発光素子の封止材として特許文献１に記載の熱硬化性エポキシ樹脂を用いると、耐熱性が不十分であるため、長期間の使用に耐えないという問題がある。特許文献２に記載の熱硬化性シリコーン樹脂を用いると、接着性や柔軟性が不十分であるため、利便性に欠けるという問題がある。また、熱硬化性樹脂自体、硬化に要する時間が長く、生産性が悪いという問題がある。
一方、特許文献３に記載の紫外線硬化性ウレタン樹脂を発光素子の封止材として使用すると、硬化に要する時間が短く、生産性が高まるが、耐熱性が十分とは言えず、熱による変色が起こり、輝度に影響する等の問題が生じることがある。
発光素子の封止材としては、耐熱性に加え、光透過性も求められ、これらを両立する新たな材料の開発が求められている。
よって、本発明の課題は、硬化に要する時間が短くて生産性を高めることができ、耐熱性及び光透過性に優れる発光素子封止材を提供し得る光硬化性樹脂組成物、及び該光硬化性樹脂組成物を用いた発光素子封止材を提供することである。 When the thermosetting epoxy resin described in Patent Document 1 is used as a sealing material for a light-emitting element, there is a problem that the heat resistance is insufficient and it cannot withstand long-term use. When the thermosetting silicone resin described in Patent Document 2 is used, there is a problem that the adhesiveness and flexibility are insufficient, and thus convenience is lacking. Further, the thermosetting resin itself has a problem that the time required for curing is long and the productivity is poor.
On the other hand, when the ultraviolet curable urethane resin described in Patent Document 3 is used as a sealing material for a light-emitting element, the time required for curing is short and the productivity is increased, but the heat resistance is not sufficient, and discoloration due to heat is caused. This may cause problems such as affecting the luminance.
As a sealing material for a light emitting element, in addition to heat resistance, light transmittance is also required, and development of a new material that satisfies both of these requirements is required.
Therefore, an object of the present invention is to provide a light-curable resin composition that can provide a light-emitting element sealing material that can improve productivity by shortening the time required for curing, and has excellent heat resistance and light transmittance, and the light. It is providing the light emitting element sealing material using a curable resin composition.
一方、特許文献３に記載の紫外線硬化性ウレタン樹脂を発光素子の封止材として使用すると、硬化に要する時間が短く、生産性が高まるが、耐熱性が十分とは言えず、熱による変色が起こり、輝度に影響する等の問題が生じることがある。
発光素子の封止材としては、耐熱性に加え、光透過性も求められ、これらを両立する新たな材料の開発が求められている。
よって、本発明の課題は、硬化に要する時間が短くて生産性を高めることができ、耐熱性及び光透過性に優れる発光素子封止材を提供し得る光硬化性樹脂組成物、及び該光硬化性樹脂組成物を用いた発光素子封止材を提供することである。 When the thermosetting epoxy resin described in Patent Document 1 is used as a sealing material for a light-emitting element, there is a problem that the heat resistance is insufficient and it cannot withstand long-term use. When the thermosetting silicone resin described in Patent Document 2 is used, there is a problem that the adhesiveness and flexibility are insufficient, and thus convenience is lacking. Further, the thermosetting resin itself has a problem that the time required for curing is long and the productivity is poor.
On the other hand, when the ultraviolet curable urethane resin described in Patent Document 3 is used as a sealing material for a light-emitting element, the time required for curing is short and the productivity is increased, but the heat resistance is not sufficient, and discoloration due to heat is caused. This may cause problems such as affecting the luminance.
As a sealing material for a light emitting element, in addition to heat resistance, light transmittance is also required, and development of a new material that satisfies both of these requirements is required.
Therefore, an object of the present invention is to provide a light-curable resin composition that can provide a light-emitting element sealing material that can improve productivity by shortening the time required for curing, and has excellent heat resistance and light transmittance, and the light. It is providing the light emitting element sealing material using a curable resin composition.
本発明者等は上記課題を解決すべく、鋭意検討した結果、末端変性水添スチレンブタジエンゴム及び特定の光重合開始剤を特定比率で含有する光硬化性樹脂組成物であれば、硬化に要する時間が短くて生産性を高めることができ、耐熱性及び光透過性が共に優れる発光素子封止材を提供できることを見出した。
As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention require curing for a photocurable resin composition containing a terminal-modified hydrogenated styrene butadiene rubber and a specific photopolymerization initiator in a specific ratio. It has been found that a light-emitting element sealing material can be provided that can improve productivity with a short time, and that is excellent in both heat resistance and light transmittance.
すなわち、本発明は、下記［１］～［５］に関する。
［１］（Ａ）末端変性水添スチレンブタジエンゴム１００質量部及び（Ｂ）α－ヒドロキシアルキルフェノン系光重合開始剤及び／又はアシルホスフィンオキシド系光重合開始剤０．１～１３質量部を含有する、光硬化性樹脂組成物。
［２］（Ａ）成分の末端変性水添スチレンブタジエンゴムが、分子の両末端に（メタ）アクリロイルオキシ基を有する水添スチレンブタジエンゴムである、上記［１］に記載の光硬化性樹脂組成物。
［３］さらに、（Ｃ）反応性希釈剤として、（メタ）アクリルモノマー及び／又はポリチオール化合物を含有する、上記［１］又は［２］に記載の光硬化性樹脂組成物。
［４］発光素子封止材用である、上記［１］～［３］のいずれかに記載の光硬化性樹脂組成物。
［５］上記［１］～［３］のいずれかに記載の光硬化性樹脂組成物を用いた発光素子封止材。 That is, the present invention relates to the following [1] to [5].
[1] Contains 100 parts by mass of (A) terminal-modified hydrogenated styrene butadiene rubber and (B) 0.1-13 parts by mass of an α-hydroxyalkylphenone photopolymerization initiator and / or an acylphosphine oxide photopolymerization initiator A photocurable resin composition.
[2] The photocurable resin composition according to the above [1], wherein the terminal-modified hydrogenated styrene butadiene rubber of the component (A) is a hydrogenated styrene butadiene rubber having (meth) acryloyloxy groups at both ends of the molecule. object.
[3] The photocurable resin composition according to the above [1] or [2], which further contains (meth) acrylic monomer and / or polythiol compound as a reactive diluent (C).
[4] The photocurable resin composition according to any one of [1] to [3], which is for a light emitting device sealing material.
[5] A light emitting device sealing material using the photocurable resin composition according to any one of [1] to [3].
［１］（Ａ）末端変性水添スチレンブタジエンゴム１００質量部及び（Ｂ）α－ヒドロキシアルキルフェノン系光重合開始剤及び／又はアシルホスフィンオキシド系光重合開始剤０．１～１３質量部を含有する、光硬化性樹脂組成物。
［２］（Ａ）成分の末端変性水添スチレンブタジエンゴムが、分子の両末端に（メタ）アクリロイルオキシ基を有する水添スチレンブタジエンゴムである、上記［１］に記載の光硬化性樹脂組成物。
［３］さらに、（Ｃ）反応性希釈剤として、（メタ）アクリルモノマー及び／又はポリチオール化合物を含有する、上記［１］又は［２］に記載の光硬化性樹脂組成物。
［４］発光素子封止材用である、上記［１］～［３］のいずれかに記載の光硬化性樹脂組成物。
［５］上記［１］～［３］のいずれかに記載の光硬化性樹脂組成物を用いた発光素子封止材。 That is, the present invention relates to the following [1] to [5].
[1] Contains 100 parts by mass of (A) terminal-modified hydrogenated styrene butadiene rubber and (B) 0.1-13 parts by mass of an α-hydroxyalkylphenone photopolymerization initiator and / or an acylphosphine oxide photopolymerization initiator A photocurable resin composition.
[2] The photocurable resin composition according to the above [1], wherein the terminal-modified hydrogenated styrene butadiene rubber of the component (A) is a hydrogenated styrene butadiene rubber having (meth) acryloyloxy groups at both ends of the molecule. object.
[3] The photocurable resin composition according to the above [1] or [2], which further contains (meth) acrylic monomer and / or polythiol compound as a reactive diluent (C).
[4] The photocurable resin composition according to any one of [1] to [3], which is for a light emitting device sealing material.
[5] A light emitting device sealing material using the photocurable resin composition according to any one of [1] to [3].
本発明の光硬化性樹脂組成物は、硬化に要する時間が短いため、生産性が高まる上、耐熱性及び光透過性に優れた発光素子封止材を提供できる。
Since the photocurable resin composition of the present invention requires a short time for curing, the productivity is enhanced and a light emitting device sealing material having excellent heat resistance and light transmittance can be provided.
［光硬化性樹脂組成物］
本発明の光硬化性樹脂組成物は、（Ａ）末端変性水添スチレンブタジエンゴム１００質量部及び（Ｂ）α－ヒドロキシアルキルフェノン系光重合開始剤及び／又はアシルホスフィンオキシド系光重合開始剤０．１～１３質量部を含有する。
（（Ａ）末端変性水添スチレンブタジエンゴム）
（Ａ）成分である末端変性水添スチレンブタジエンゴムは、水添スチレンブタジエンゴムの両末端が、（メタ）アクリロイル基等の光硬化性官能基で置換されたものが好ましい。
該末端変性水添スチレンブタジエンゴムの製造方法としては特に制限はないが、例えば、未変性の水添スチレンブタジエンゴムとエチレンオキシド又はプロピレンオキシドとを反応させることにより、分子末端に水酸基を導入し、さらに（メタ）アクリロイル基等の光硬化性官能基を有する化合物と反応させる方法が好ましい。 [Photocurable resin composition]
The photocurable resin composition of the present invention comprises (A) 100 parts by mass of a terminal-modified hydrogenated styrene butadiene rubber and (B) an α-hydroxyalkylphenone photopolymerization initiator and / or an acylphosphine oxide photopolymerization initiator 0. 1 to 13 parts by mass are contained.
((A) terminal-modified hydrogenated styrene butadiene rubber)
The terminal-modified hydrogenated styrene butadiene rubber as the component (A) is preferably one in which both ends of the hydrogenated styrene butadiene rubber are substituted with a photocurable functional group such as a (meth) acryloyl group.
The method for producing the terminal-modified hydrogenated styrene butadiene rubber is not particularly limited. For example, a hydroxyl group is introduced into the molecular terminal by reacting an unmodified hydrogenated styrene butadiene rubber with ethylene oxide or propylene oxide. A method of reacting with a compound having a photocurable functional group such as a (meth) acryloyl group is preferred.
本発明の光硬化性樹脂組成物は、（Ａ）末端変性水添スチレンブタジエンゴム１００質量部及び（Ｂ）α－ヒドロキシアルキルフェノン系光重合開始剤及び／又はアシルホスフィンオキシド系光重合開始剤０．１～１３質量部を含有する。
（（Ａ）末端変性水添スチレンブタジエンゴム）
（Ａ）成分である末端変性水添スチレンブタジエンゴムは、水添スチレンブタジエンゴムの両末端が、（メタ）アクリロイル基等の光硬化性官能基で置換されたものが好ましい。
該末端変性水添スチレンブタジエンゴムの製造方法としては特に制限はないが、例えば、未変性の水添スチレンブタジエンゴムとエチレンオキシド又はプロピレンオキシドとを反応させることにより、分子末端に水酸基を導入し、さらに（メタ）アクリロイル基等の光硬化性官能基を有する化合物と反応させる方法が好ましい。 [Photocurable resin composition]
The photocurable resin composition of the present invention comprises (A) 100 parts by mass of a terminal-modified hydrogenated styrene butadiene rubber and (B) an α-hydroxyalkylphenone photopolymerization initiator and / or an acylphosphine oxide photopolymerization initiator 0. 1 to 13 parts by mass are contained.
((A) terminal-modified hydrogenated styrene butadiene rubber)
The terminal-modified hydrogenated styrene butadiene rubber as the component (A) is preferably one in which both ends of the hydrogenated styrene butadiene rubber are substituted with a photocurable functional group such as a (meth) acryloyl group.
The method for producing the terminal-modified hydrogenated styrene butadiene rubber is not particularly limited. For example, a hydroxyl group is introduced into the molecular terminal by reacting an unmodified hydrogenated styrene butadiene rubber with ethylene oxide or propylene oxide. A method of reacting with a compound having a photocurable functional group such as a (meth) acryloyl group is preferred.
上記光硬化性官能基を有する化合物との反応としては、例えば、分子末端に水酸基が導入された水添スチレンブタジエンゴムと２－（メタ）アクリロイルオキシエチルイソシアネート等によるウレタン化反応；分子末端に水酸基が導入された水添スチレンブタジエンゴムとメチル（メタ）アクリレート、エチル（メタ）アクリレート、イソプロピル（メタ）アクリレート等の低級アルキル（メタ）アクリレートによるエステル交換反応；分子末端に水酸基が導入された水添スチレンブタジエンゴムをイソシアネート化合物と反応させて得られるプレポリマーと２－ヒドロキシエチルアクリレート等との反応等により、末端変性水添スチレンブタジエンゴムを得ることができる。
なお、末端変性水添スチレンブタジエンゴムとしては、分子の両末端に（メタ）アクリロイルオキシ基を有する水添スチレンブタジエンゴムを使用することが好ましい。 Examples of the reaction with the compound having a photocurable functional group include a urethanation reaction with a hydrogenated styrene butadiene rubber having a hydroxyl group introduced at the molecular terminal and 2- (meth) acryloyloxyethyl isocyanate; a hydroxyl group at the molecular terminal Transesterification reaction of hydrogenated styrene butadiene rubber with methyl introduced and lower alkyl (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, etc .; A terminal-modified hydrogenated styrene butadiene rubber can be obtained by a reaction of a prepolymer obtained by reacting a styrene butadiene rubber with an isocyanate compound and 2-hydroxyethyl acrylate.
The terminal-modified hydrogenated styrene butadiene rubber is preferably a hydrogenated styrene butadiene rubber having (meth) acryloyloxy groups at both ends of the molecule.
なお、末端変性水添スチレンブタジエンゴムとしては、分子の両末端に（メタ）アクリロイルオキシ基を有する水添スチレンブタジエンゴムを使用することが好ましい。 Examples of the reaction with the compound having a photocurable functional group include a urethanation reaction with a hydrogenated styrene butadiene rubber having a hydroxyl group introduced at the molecular terminal and 2- (meth) acryloyloxyethyl isocyanate; a hydroxyl group at the molecular terminal Transesterification reaction of hydrogenated styrene butadiene rubber with methyl introduced and lower alkyl (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, etc .; A terminal-modified hydrogenated styrene butadiene rubber can be obtained by a reaction of a prepolymer obtained by reacting a styrene butadiene rubber with an isocyanate compound and 2-hydroxyethyl acrylate.
The terminal-modified hydrogenated styrene butadiene rubber is preferably a hydrogenated styrene butadiene rubber having (meth) acryloyloxy groups at both ends of the molecule.
なお、上記の未変性の水添スチレンブタジエンゴムは、スチレンブタジエンゴム又は分子末端に水酸基が導入されたスチレンブタジエンゴムを水素添加することにより得ることができる。ここで、原料のスチレンブタジエンゴムは、スチレンとブタジエンの共重合により得ることができ、例えば、ナフタレンジリチウム、ジリチオヘキシルベンゼン等の公知のジリチウム化合物及び反応に不活性な溶媒の存在下、１０～８０℃にてスチレンと１，３－ブタジエンを共重合させる方法が挙げられる。
スチレンブタジエンゴム又は分子末端に水酸基が導入されたスチレンブタジエンゴムを水素添加する方法に特に制限は無く、公知の方法を利用することができる。例えば、シクロヘキサン等の飽和炭化水素溶液中で、スチレンブタジエンゴムを、ラネーニッケル又はＰｔ、Ｐｄ、Ｒｕ、Ｒｈ、Ｎｉ等の金属をカーボン、アルミナ、硅藻土等の担体に担持させた不均一触媒：ニッケル、コバルト等の第８～１０族金属からなる有機金属化合物とトリエチルアルミニウム、トリイソブチルアルミニウム等の有機アルミニウム化合物又は有機リチウム化合物等の組み合わせからなるチーグラー系の触媒：チタン、ジルコニウム、ハフニウム等の遷移金属のビス（シクロペンタジエニル）化合物とリチウム、ナトリウム、カリウム、アルミニウム、亜鉛又はマグネシウム等の有機金属化合物の組み合わせからなるメタロセン系触媒等の公知の水素添加触媒の存在下及び水素加圧下に５０～１８０℃で反応させることにより、共役ジエン部位の一部又は全部を水素添加することができる。
スチレンブタジエンゴム又は分子末端に水酸基が導入されたスチレンブタジエンゴムの水素添加率に特に制限は無いが、耐熱性の観点から、好ましくは８０～１００％、より好ましくは９０～１００％である。 The unmodified hydrogenated styrene butadiene rubber can be obtained by hydrogenating a styrene butadiene rubber or a styrene butadiene rubber having a hydroxyl group introduced at the molecular end. Here, the raw material styrene-butadiene rubber can be obtained by copolymerization of styrene and butadiene. For example, in the presence of a known dilithium compound such as naphthalene dilithium and dilithiohexylbenzene and a solvent inert to the reaction, 10 Examples include a method of copolymerizing styrene and 1,3-butadiene at -80 ° C.
There is no particular limitation on the method of hydrogenating the styrene butadiene rubber or the styrene butadiene rubber having a hydroxyl group introduced at the molecular end, and a known method can be used. For example, in a saturated hydrocarbon solution such as cyclohexane, a heterogeneous catalyst in which styrene butadiene rubber is supported on a carrier such as Raney nickel or Pt, Pd, Ru, Rh, Ni on a support such as carbon, alumina, diatomaceous earth: Ziegler-type catalyst consisting of a combination of organometallic compounds consisting of Group 8-10 metals such as nickel and cobalt and organoaluminum compounds such as triethylaluminum and triisobutylaluminum or organolithium compounds: transitions such as titanium, zirconium and hafnium 50 in the presence of a known hydrogenation catalyst such as a metallocene catalyst comprising a combination of a metal bis (cyclopentadienyl) compound and an organometallic compound such as lithium, sodium, potassium, aluminum, zinc or magnesium, and under hydrogen pressure. React at ~ 180 ℃ Accordingly, some or all of the conjugated diene portion can be hydrogenated.
The hydrogenation rate of the styrene butadiene rubber or the styrene butadiene rubber having a hydroxyl group introduced at the molecular end is not particularly limited, but is preferably 80 to 100%, more preferably 90 to 100% from the viewpoint of heat resistance.
スチレンブタジエンゴム又は分子末端に水酸基が導入されたスチレンブタジエンゴムを水素添加する方法に特に制限は無く、公知の方法を利用することができる。例えば、シクロヘキサン等の飽和炭化水素溶液中で、スチレンブタジエンゴムを、ラネーニッケル又はＰｔ、Ｐｄ、Ｒｕ、Ｒｈ、Ｎｉ等の金属をカーボン、アルミナ、硅藻土等の担体に担持させた不均一触媒：ニッケル、コバルト等の第８～１０族金属からなる有機金属化合物とトリエチルアルミニウム、トリイソブチルアルミニウム等の有機アルミニウム化合物又は有機リチウム化合物等の組み合わせからなるチーグラー系の触媒：チタン、ジルコニウム、ハフニウム等の遷移金属のビス（シクロペンタジエニル）化合物とリチウム、ナトリウム、カリウム、アルミニウム、亜鉛又はマグネシウム等の有機金属化合物の組み合わせからなるメタロセン系触媒等の公知の水素添加触媒の存在下及び水素加圧下に５０～１８０℃で反応させることにより、共役ジエン部位の一部又は全部を水素添加することができる。
スチレンブタジエンゴム又は分子末端に水酸基が導入されたスチレンブタジエンゴムの水素添加率に特に制限は無いが、耐熱性の観点から、好ましくは８０～１００％、より好ましくは９０～１００％である。 The unmodified hydrogenated styrene butadiene rubber can be obtained by hydrogenating a styrene butadiene rubber or a styrene butadiene rubber having a hydroxyl group introduced at the molecular end. Here, the raw material styrene-butadiene rubber can be obtained by copolymerization of styrene and butadiene. For example, in the presence of a known dilithium compound such as naphthalene dilithium and dilithiohexylbenzene and a solvent inert to the reaction, 10 Examples include a method of copolymerizing styrene and 1,3-butadiene at -80 ° C.
There is no particular limitation on the method of hydrogenating the styrene butadiene rubber or the styrene butadiene rubber having a hydroxyl group introduced at the molecular end, and a known method can be used. For example, in a saturated hydrocarbon solution such as cyclohexane, a heterogeneous catalyst in which styrene butadiene rubber is supported on a carrier such as Raney nickel or Pt, Pd, Ru, Rh, Ni on a support such as carbon, alumina, diatomaceous earth: Ziegler-type catalyst consisting of a combination of organometallic compounds consisting of Group 8-10 metals such as nickel and cobalt and organoaluminum compounds such as triethylaluminum and triisobutylaluminum or organolithium compounds: transitions such as titanium, zirconium and hafnium 50 in the presence of a known hydrogenation catalyst such as a metallocene catalyst comprising a combination of a metal bis (cyclopentadienyl) compound and an organometallic compound such as lithium, sodium, potassium, aluminum, zinc or magnesium, and under hydrogen pressure. React at ~ 180 ℃ Accordingly, some or all of the conjugated diene portion can be hydrogenated.
The hydrogenation rate of the styrene butadiene rubber or the styrene butadiene rubber having a hydroxyl group introduced at the molecular end is not particularly limited, but is preferably 80 to 100%, more preferably 90 to 100% from the viewpoint of heat resistance.
末端変性水添スチレンブタジエンゴムの重量平均分子量は、好ましくは５，０００～４０，０００、より好ましくは１０，０００～３０，０００、さらに好ましくは１５，０００～２０，０００である。なお、本明細書において、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、単分散ポリスチレンを基準としてポリスチレン換算で求めた値である。
また、分子量分布（Ｍｗ／Ｍｎ）は、好ましくは３以下、より好ましくは２以下、さらに好ましくは１．２以下である。末端変性水添スチレンブタジエンゴムの重量平均分子量がこの範囲内であると、末端変性水添スチレンブタジエンゴムの粘度が高くなり過ぎず、取り扱い性が良い。また、分子量分布が３以下であれば、量産する場合に再現性を得やすく、同程度の分子量の共重合体を得ることが容易になる。
末端変性水添スチレンブタジエンゴムのスチレン由来の構成単位の含有量（以下、スチレン含有量と称する。）に特に制限はないが、全構成単位に対して、好ましくは１０～４０質量％、より好ましくは１０～３０質量％である。 The weight average molecular weight of the terminal-modified hydrogenated styrene butadiene rubber is preferably 5,000 to 40,000, more preferably 10,000 to 30,000, and still more preferably 15,000 to 20,000. In addition, in this specification, a weight average molecular weight is the value calculated | required by polystyrene conversion on the basis of the monodispersed polystyrene by the gel permeation chromatography (GPC).
The molecular weight distribution (Mw / Mn) is preferably 3 or less, more preferably 2 or less, and still more preferably 1.2 or less. When the weight average molecular weight of the terminal-modified hydrogenated styrene butadiene rubber is within this range, the viscosity of the terminal-modified hydrogenated styrene butadiene rubber does not become too high, and the handleability is good. Moreover, if the molecular weight distribution is 3 or less, it is easy to obtain reproducibility in mass production, and it becomes easy to obtain a copolymer having the same molecular weight.
The content of the structural unit derived from styrene in the terminal-modified hydrogenated styrene-butadiene rubber (hereinafter referred to as styrene content) is not particularly limited, but is preferably 10 to 40% by mass, more preferably based on the total structural unit. Is 10 to 30% by mass.
また、分子量分布（Ｍｗ／Ｍｎ）は、好ましくは３以下、より好ましくは２以下、さらに好ましくは１．２以下である。末端変性水添スチレンブタジエンゴムの重量平均分子量がこの範囲内であると、末端変性水添スチレンブタジエンゴムの粘度が高くなり過ぎず、取り扱い性が良い。また、分子量分布が３以下であれば、量産する場合に再現性を得やすく、同程度の分子量の共重合体を得ることが容易になる。
末端変性水添スチレンブタジエンゴムのスチレン由来の構成単位の含有量（以下、スチレン含有量と称する。）に特に制限はないが、全構成単位に対して、好ましくは１０～４０質量％、より好ましくは１０～３０質量％である。 The weight average molecular weight of the terminal-modified hydrogenated styrene butadiene rubber is preferably 5,000 to 40,000, more preferably 10,000 to 30,000, and still more preferably 15,000 to 20,000. In addition, in this specification, a weight average molecular weight is the value calculated | required by polystyrene conversion on the basis of the monodispersed polystyrene by the gel permeation chromatography (GPC).
The molecular weight distribution (Mw / Mn) is preferably 3 or less, more preferably 2 or less, and still more preferably 1.2 or less. When the weight average molecular weight of the terminal-modified hydrogenated styrene butadiene rubber is within this range, the viscosity of the terminal-modified hydrogenated styrene butadiene rubber does not become too high, and the handleability is good. Moreover, if the molecular weight distribution is 3 or less, it is easy to obtain reproducibility in mass production, and it becomes easy to obtain a copolymer having the same molecular weight.
The content of the structural unit derived from styrene in the terminal-modified hydrogenated styrene-butadiene rubber (hereinafter referred to as styrene content) is not particularly limited, but is preferably 10 to 40% by mass, more preferably based on the total structural unit. Is 10 to 30% by mass.
（（Ｂ）α－ヒドロキシアルキルフェノン系光重合開始剤及び／又はアシルホスフィンオキシド系光重合開始剤）
本発明の光硬化性樹脂組成物は、（Ｂ）成分として、α－ヒドロキシアルキルフェノン系光重合開始剤及びアシルホスフィンオキシド系光重合開始剤のうち、少なくとも一方を含有する。
α－ヒドロキシアルキルフェノン系光重合開始剤としては、下記一般式（Ｉ）で表されるものが好ましい。 ((B) α-hydroxyalkylphenone photopolymerization initiator and / or acylphosphine oxide photopolymerization initiator)
The photocurable resin composition of the present invention contains at least one of an α-hydroxyalkylphenone photopolymerization initiator and an acylphosphine oxide photopolymerization initiator as component (B).
As the α-hydroxyalkylphenone photopolymerization initiator, those represented by the following general formula (I) are preferable.
本発明の光硬化性樹脂組成物は、（Ｂ）成分として、α－ヒドロキシアルキルフェノン系光重合開始剤及びアシルホスフィンオキシド系光重合開始剤のうち、少なくとも一方を含有する。
α－ヒドロキシアルキルフェノン系光重合開始剤としては、下記一般式（Ｉ）で表されるものが好ましい。 ((B) α-hydroxyalkylphenone photopolymerization initiator and / or acylphosphine oxide photopolymerization initiator)
The photocurable resin composition of the present invention contains at least one of an α-hydroxyalkylphenone photopolymerization initiator and an acylphosphine oxide photopolymerization initiator as component (B).
As the α-hydroxyalkylphenone photopolymerization initiator, those represented by the following general formula (I) are preferable.
上記一般式中、Ｒ1、Ｒ1'、Ｒ2及びＲ2'は、それぞれ独立して、炭素数１～５のアルキル基を表すか、Ｒ1とＲ2、Ｒ1'とＲ2'とが一緒になって炭素数１～５のアルキレン基を表す。Ｒ1とＲ1'、Ｒ2とＲ2'は、それぞれ同一であってもよいし、異なっていてもよい。また、Ｗ、Ｚ及びＺ’は、それぞれ独立して、炭素数１～５のアルキレン基を表す。ＺとＺ’は、同一であってもよいし、異なっていてもよい。ｍは、０又は１である。ｎ１及びｎ２は、それぞれ独立して、０又は１を表す。
Ｒ1、Ｒ1'、Ｒ2及びＲ2'がそれぞれ独立して表す炭素数１～５のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｔ－ブチル基等が挙げられる。これらの中でも、炭素数１～３のアルキル基が好ましく、メチル基がより好ましい。
Ｒ1とＲ2、Ｒ1'とＲ2'とが一緒になって表す炭素数１～５のアルキレン基としては、メチレン基、エチレン基、テトラメチレン基、ペンタメチレン基等が挙げられる。これらの中でも、ペンタメチレン基が好ましい。
Ｗ、Ｚ及びＺ’がそれぞれ独立して表す炭素数１～５のアルキレン基としては、メチレン基、エチレン基、トリメチレン基等が挙げられる。Ｗとしては、メチレン基が好ましい。Ｚ及びＺ’としては、いずれもメチレン基又はエチレン基であることが好ましく、いずれもエチレン基であることがより好ましい。
一般式（Ｉ）で表されるα－ヒドロキシアルキルフェノン系光重合開始剤の好ましい具体例を以下に示すが、特にこれらに制限されるものではない。 In the above general formula, R 1 , R 1 ′ , R 2 and R 2 ′ each independently represent an alkyl group having 1 to 5 carbon atoms, or R 1 and R 2 , R 1 ′ and R 2 ′. Together represent an alkylene group having 1 to 5 carbon atoms. R 1 and R 1 ′ , R 2 and R 2 ′ may be the same or different. W, Z and Z ′ each independently represents an alkylene group having 1 to 5 carbon atoms. Z and Z ′ may be the same or different. m is 0 or 1. n1 and n2 each independently represents 0 or 1.
Examples of the alkyl group having 1 to 5 carbon atoms independently represented by R 1 , R 1 ′ , R 2 and R 2 ′ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group and the like. Can be mentioned. Among these, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
Examples of the alkylene group having 1 to 5 carbon atoms represented by R 1 and R 2 and R 1 ′ and R 2 ′ together include a methylene group, an ethylene group, a tetramethylene group, and a pentamethylene group. Among these, a pentamethylene group is preferable.
Examples of the alkylene group having 1 to 5 carbon atoms each independently represented by W, Z and Z ′ include a methylene group, an ethylene group and a trimethylene group. W is preferably a methylene group. As Z and Z ′, both are preferably a methylene group or an ethylene group, more preferably an ethylene group.
Preferred specific examples of the α-hydroxyalkylphenone photopolymerization initiator represented by the general formula (I) are shown below, but are not particularly limited thereto.
Ｒ1、Ｒ1'、Ｒ2及びＲ2'がそれぞれ独立して表す炭素数１～５のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｔ－ブチル基等が挙げられる。これらの中でも、炭素数１～３のアルキル基が好ましく、メチル基がより好ましい。
Ｒ1とＲ2、Ｒ1'とＲ2'とが一緒になって表す炭素数１～５のアルキレン基としては、メチレン基、エチレン基、テトラメチレン基、ペンタメチレン基等が挙げられる。これらの中でも、ペンタメチレン基が好ましい。
Ｗ、Ｚ及びＺ’がそれぞれ独立して表す炭素数１～５のアルキレン基としては、メチレン基、エチレン基、トリメチレン基等が挙げられる。Ｗとしては、メチレン基が好ましい。Ｚ及びＺ’としては、いずれもメチレン基又はエチレン基であることが好ましく、いずれもエチレン基であることがより好ましい。
一般式（Ｉ）で表されるα－ヒドロキシアルキルフェノン系光重合開始剤の好ましい具体例を以下に示すが、特にこれらに制限されるものではない。 In the above general formula, R 1 , R 1 ′ , R 2 and R 2 ′ each independently represent an alkyl group having 1 to 5 carbon atoms, or R 1 and R 2 , R 1 ′ and R 2 ′. Together represent an alkylene group having 1 to 5 carbon atoms. R 1 and R 1 ′ , R 2 and R 2 ′ may be the same or different. W, Z and Z ′ each independently represents an alkylene group having 1 to 5 carbon atoms. Z and Z ′ may be the same or different. m is 0 or 1. n1 and n2 each independently represents 0 or 1.
Examples of the alkyl group having 1 to 5 carbon atoms independently represented by R 1 , R 1 ′ , R 2 and R 2 ′ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group and the like. Can be mentioned. Among these, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
Examples of the alkylene group having 1 to 5 carbon atoms represented by R 1 and R 2 and R 1 ′ and R 2 ′ together include a methylene group, an ethylene group, a tetramethylene group, and a pentamethylene group. Among these, a pentamethylene group is preferable.
Examples of the alkylene group having 1 to 5 carbon atoms each independently represented by W, Z and Z ′ include a methylene group, an ethylene group and a trimethylene group. W is preferably a methylene group. As Z and Z ′, both are preferably a methylene group or an ethylene group, more preferably an ethylene group.
Preferred specific examples of the α-hydroxyalkylphenone photopolymerization initiator represented by the general formula (I) are shown below, but are not particularly limited thereto.
アシルホスフィンオキシド系光重合開始剤としては、例えば下記一般式（II）又は（III）で表わされるものが好ましい。
As the acylphosphine oxide photopolymerization initiator, for example, those represented by the following general formula (II) or (III) are preferable.
上記一般式中、Ｒ3、Ｒ3'及びＲ3''は、それぞれ独立して、炭素数１～５のアルキル基、炭素数１～５のアルコキシ基を表す。Ｒ4は、炭素数１～１５のアルキル基を表す。ｐ１、ｐ２及びｐ３は、それぞれ独立して、０～３の整数を表す。ｑは、０又は１を表す。
Ｒ3、Ｒ3'及びＲ3''がそれぞれ独立して表す炭素数１～５のアルキル基としては、メチル基、エチル基、各種プロピル基（「各種」とは、直鎖及びあらゆる分岐鎖を含むことを示す。以下同様。）、各種ブチル基等が挙げられる。これらの中でも、メチル基が好ましい。Ｒ3、Ｒ3'及びＲ3''がそれぞれ独立して表す炭素数１～５のアルコキシ基としては、メトキシ基、エトキシ基等が挙げられる。これらの中でもメトキシ基が好ましい。
Ｒ4が表す炭素数１～１５のアルキル基としては、メチル基、エチル基、各種プロピル基、各種ブチル基、各種ヘキシル基、各種オクチル基、各種デシル基、各種ドデシル基等が挙げられる。これらの中でも、炭素数１～１０のアルキル基が好ましく、炭素数４～１０のアルキル基がより好ましく、炭素数５～８のアルキル基がさらに好ましい。
一般式（II）において、ｐ１は、３が好ましい。ｐ２は、ｑが０である場合は、０が好ましく、ｑが１である場合は、３が好ましい。ｐ３は、０が好ましい。また、一般式（III）においては、ｐ１及びｐ２は、いずれも２が好ましい。
一般式（II）で表されるアシルホスフィンオキシド系光重合開始剤の好ましい具体例を以下に示すが、特にこれらに制限されるものではない。 In the above general formula, R 3 , R 3 ′ and R 3 ″ each independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. R 4 represents an alkyl group having 1 to 15 carbon atoms. p1, p2 and p3 each independently represents an integer of 0 to 3. q represents 0 or 1;
Examples of the alkyl group having 1 to 5 carbon atoms independently represented by R 3 , R 3 ′, and R 3 ″ include a methyl group, an ethyl group, and various propyl groups (“various” means linear and all branched chains). The same applies hereinafter), and various butyl groups. Among these, a methyl group is preferable. Examples of the alkoxy group having 1 to 5 carbon atoms independently represented by R 3 , R 3 ′ and R 3 ″ include a methoxy group and an ethoxy group. Among these, a methoxy group is preferable.
Examples of the alkyl group having 1 to 15 carbon atoms represented by R 4 include a methyl group, an ethyl group, various propyl groups, various butyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, and the like. Among these, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 4 to 10 carbon atoms is more preferable, and an alkyl group having 5 to 8 carbon atoms is more preferable.
In general formula (II), p1 is preferably 3. p2 is preferably 0 when q is 0, and preferably 3 when q is 1. p3 is preferably 0. In general formula (III), both p1 and p2 are preferably 2.
Preferable specific examples of the acylphosphine oxide photopolymerization initiator represented by the general formula (II) are shown below, but are not particularly limited thereto.
Ｒ3、Ｒ3'及びＲ3''がそれぞれ独立して表す炭素数１～５のアルキル基としては、メチル基、エチル基、各種プロピル基（「各種」とは、直鎖及びあらゆる分岐鎖を含むことを示す。以下同様。）、各種ブチル基等が挙げられる。これらの中でも、メチル基が好ましい。Ｒ3、Ｒ3'及びＲ3''がそれぞれ独立して表す炭素数１～５のアルコキシ基としては、メトキシ基、エトキシ基等が挙げられる。これらの中でもメトキシ基が好ましい。
Ｒ4が表す炭素数１～１５のアルキル基としては、メチル基、エチル基、各種プロピル基、各種ブチル基、各種ヘキシル基、各種オクチル基、各種デシル基、各種ドデシル基等が挙げられる。これらの中でも、炭素数１～１０のアルキル基が好ましく、炭素数４～１０のアルキル基がより好ましく、炭素数５～８のアルキル基がさらに好ましい。
一般式（II）において、ｐ１は、３が好ましい。ｐ２は、ｑが０である場合は、０が好ましく、ｑが１である場合は、３が好ましい。ｐ３は、０が好ましい。また、一般式（III）においては、ｐ１及びｐ２は、いずれも２が好ましい。
一般式（II）で表されるアシルホスフィンオキシド系光重合開始剤の好ましい具体例を以下に示すが、特にこれらに制限されるものではない。 In the above general formula, R 3 , R 3 ′ and R 3 ″ each independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. R 4 represents an alkyl group having 1 to 15 carbon atoms. p1, p2 and p3 each independently represents an integer of 0 to 3. q represents 0 or 1;
Examples of the alkyl group having 1 to 5 carbon atoms independently represented by R 3 , R 3 ′, and R 3 ″ include a methyl group, an ethyl group, and various propyl groups (“various” means linear and all branched chains). The same applies hereinafter), and various butyl groups. Among these, a methyl group is preferable. Examples of the alkoxy group having 1 to 5 carbon atoms independently represented by R 3 , R 3 ′ and R 3 ″ include a methoxy group and an ethoxy group. Among these, a methoxy group is preferable.
Examples of the alkyl group having 1 to 15 carbon atoms represented by R 4 include a methyl group, an ethyl group, various propyl groups, various butyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, and the like. Among these, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 4 to 10 carbon atoms is more preferable, and an alkyl group having 5 to 8 carbon atoms is more preferable.
In general formula (II), p1 is preferably 3. p2 is preferably 0 when q is 0, and preferably 3 when q is 1. p3 is preferably 0. In general formula (III), both p1 and p2 are preferably 2.
Preferable specific examples of the acylphosphine oxide photopolymerization initiator represented by the general formula (II) are shown below, but are not particularly limited thereto.
（Ｂ）成分の光重合開始剤が前記２種類であるのは、これらを含有する光硬化性樹脂組成物を用いて得られる発光素子封止材の光透過性が極めて優れているためである。なお、その他の光重合開始剤、例えばベンジルジメチルケタールや、α－アミノアルキルフェノン系光重合開始剤、オキシフェニル酢酸エステル系光重合開始剤等では、光硬化性樹脂組成物から得られる硬化物の光透過性に乏しく、発光素子封止材として有用ではないことが判明した。
但し、本発明の光硬化性樹脂組成物は、これらのその他の光重合開始剤を、本発明の効果が失われない程度において含有してもよい。これらのその他の光重合開始剤を含有する場合、その含有量は、発光素子封止材の光透過性の観点から、（Ａ）成分１００質量部に対して好ましくは５質量部以下、より好ましくは３質量部以下、さらに好ましくは１質量部以下である。 The reason why the photopolymerization initiator of component (B) is the above-mentioned two types is that the light transmittance of the light-emitting element sealing material obtained by using the photocurable resin composition containing these is extremely excellent. . Other photopolymerization initiators such as benzyl dimethyl ketal, α-aminoalkylphenone photopolymerization initiators, oxyphenylacetic acid ester photopolymerization initiators, and the like are used for cured products obtained from photocurable resin compositions. It was found that the light transmittance was poor and it was not useful as a light emitting device sealing material.
However, the photocurable resin composition of the present invention may contain these other photopolymerization initiators as long as the effects of the present invention are not lost. When these other photopolymerization initiators are contained, the content thereof is preferably 5 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of component (A), from the viewpoint of light transmittance of the light emitting device sealing material. Is 3 parts by mass or less, more preferably 1 part by mass or less.
但し、本発明の光硬化性樹脂組成物は、これらのその他の光重合開始剤を、本発明の効果が失われない程度において含有してもよい。これらのその他の光重合開始剤を含有する場合、その含有量は、発光素子封止材の光透過性の観点から、（Ａ）成分１００質量部に対して好ましくは５質量部以下、より好ましくは３質量部以下、さらに好ましくは１質量部以下である。 The reason why the photopolymerization initiator of component (B) is the above-mentioned two types is that the light transmittance of the light-emitting element sealing material obtained by using the photocurable resin composition containing these is extremely excellent. . Other photopolymerization initiators such as benzyl dimethyl ketal, α-aminoalkylphenone photopolymerization initiators, oxyphenylacetic acid ester photopolymerization initiators, and the like are used for cured products obtained from photocurable resin compositions. It was found that the light transmittance was poor and it was not useful as a light emitting device sealing material.
However, the photocurable resin composition of the present invention may contain these other photopolymerization initiators as long as the effects of the present invention are not lost. When these other photopolymerization initiators are contained, the content thereof is preferably 5 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of component (A), from the viewpoint of light transmittance of the light emitting device sealing material. Is 3 parts by mass or less, more preferably 1 part by mass or less.
（（Ｃ）反応性希釈剤）
本発明の光硬化性樹脂組成物は、さらに反応性希釈剤を含有していてもよい。
反応性希釈剤としては、液体光重合性モノビニルモノマーを用いることができる。反応性希釈剤は、光硬化性樹脂組成物の粘度を低下させ、塗布を容易にするものであり、光硬化性樹脂組成物の光硬化の際に重合し得るものである。
反応性希釈剤としては、具体的には、酢酸ビニル等のビニルエステル、（メタ）アクリルモノマー、Ｎ－ビニルモノマー、ポリチオール化合物等が挙げられる。
（メタ）アクリルモノマーとしては、例えば、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ｎ－オクタデシル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、（メタ）アクリル酸と多価アルコールとのエステル等が挙げられる。 ((C) Reactive diluent)
The photocurable resin composition of the present invention may further contain a reactive diluent.
As the reactive diluent, a liquid photopolymerizable monovinyl monomer can be used. The reactive diluent reduces the viscosity of the photocurable resin composition and facilitates application, and can be polymerized when the photocurable resin composition is photocured.
Specific examples of the reactive diluent include vinyl esters such as vinyl acetate, (meth) acrylic monomers, N-vinyl monomers, polythiol compounds, and the like.
Examples of the (meth) acrylic monomer include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, n-octadecyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl ( Examples include (meth) acrylates and esters of (meth) acrylic acid and polyhydric alcohols.
本発明の光硬化性樹脂組成物は、さらに反応性希釈剤を含有していてもよい。
反応性希釈剤としては、液体光重合性モノビニルモノマーを用いることができる。反応性希釈剤は、光硬化性樹脂組成物の粘度を低下させ、塗布を容易にするものであり、光硬化性樹脂組成物の光硬化の際に重合し得るものである。
反応性希釈剤としては、具体的には、酢酸ビニル等のビニルエステル、（メタ）アクリルモノマー、Ｎ－ビニルモノマー、ポリチオール化合物等が挙げられる。
（メタ）アクリルモノマーとしては、例えば、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ｎ－オクタデシル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、（メタ）アクリル酸と多価アルコールとのエステル等が挙げられる。 ((C) Reactive diluent)
The photocurable resin composition of the present invention may further contain a reactive diluent.
As the reactive diluent, a liquid photopolymerizable monovinyl monomer can be used. The reactive diluent reduces the viscosity of the photocurable resin composition and facilitates application, and can be polymerized when the photocurable resin composition is photocured.
Specific examples of the reactive diluent include vinyl esters such as vinyl acetate, (meth) acrylic monomers, N-vinyl monomers, polythiol compounds, and the like.
Examples of the (meth) acrylic monomer include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, n-octadecyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl ( Examples include (meth) acrylates and esters of (meth) acrylic acid and polyhydric alcohols.
Ｎ－ビニルモノマーとしては、例えばＮ，Ｎ－ジメチルアクリルアミド、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム等が挙げられる。
ポリチオール化合物としては、分子内にメルカプト基を２～６個有するものであれば特に制限はなく、例えば、炭素数２～２０程度のアルカンジチオール等の脂肪族ポリチオール類；キシリレンジチオール等の芳香族ポリチオール類；アルコール類のハロヒドリン付加物のハロゲン原子をメルカプト基で置換してなるポリチオール類；ポリエポキシド化合物の硫化水素反応生成物からなるポリチオール類；分子内に水酸基２～６個を有する多価アルコール類と、チオグリコール酸、β－メルカプトプロピオン酸、又はβ－メルカプトブタン酸とのエステル化物からなるポリチオール類等が挙げられる。
光硬化性樹脂組成物に（Ｃ）成分を含有させる場合、その含有量は、光硬化性樹脂組成物に対して、好ましくは５～７０質量％、より好ましくは１０～５０質量％である。 Examples of the N-vinyl monomer include N, N-dimethylacrylamide, N-vinylpyrrolidone, N-vinylcaprolactam and the like.
The polythiol compound is not particularly limited as long as it has 2 to 6 mercapto groups in the molecule. For example, aliphatic polythiols such as alkanedithiol having about 2 to 20 carbon atoms; aromatics such as xylylenedithiol Polythiols; polythiols obtained by substituting halogen atoms of halohydrin adducts of alcohols with mercapto groups; polythiols comprising hydrogen sulfide reaction products of polyepoxide compounds; polyhydric alcohols having 2 to 6 hydroxyl groups in the molecule And polythiols formed by esterification with thioglycolic acid, β-mercaptopropionic acid, or β-mercaptobutanoic acid.
When the component (C) is contained in the photocurable resin composition, the content thereof is preferably 5 to 70% by mass, more preferably 10 to 50% by mass with respect to the photocurable resin composition.
ポリチオール化合物としては、分子内にメルカプト基を２～６個有するものであれば特に制限はなく、例えば、炭素数２～２０程度のアルカンジチオール等の脂肪族ポリチオール類；キシリレンジチオール等の芳香族ポリチオール類；アルコール類のハロヒドリン付加物のハロゲン原子をメルカプト基で置換してなるポリチオール類；ポリエポキシド化合物の硫化水素反応生成物からなるポリチオール類；分子内に水酸基２～６個を有する多価アルコール類と、チオグリコール酸、β－メルカプトプロピオン酸、又はβ－メルカプトブタン酸とのエステル化物からなるポリチオール類等が挙げられる。
光硬化性樹脂組成物に（Ｃ）成分を含有させる場合、その含有量は、光硬化性樹脂組成物に対して、好ましくは５～７０質量％、より好ましくは１０～５０質量％である。 Examples of the N-vinyl monomer include N, N-dimethylacrylamide, N-vinylpyrrolidone, N-vinylcaprolactam and the like.
The polythiol compound is not particularly limited as long as it has 2 to 6 mercapto groups in the molecule. For example, aliphatic polythiols such as alkanedithiol having about 2 to 20 carbon atoms; aromatics such as xylylenedithiol Polythiols; polythiols obtained by substituting halogen atoms of halohydrin adducts of alcohols with mercapto groups; polythiols comprising hydrogen sulfide reaction products of polyepoxide compounds; polyhydric alcohols having 2 to 6 hydroxyl groups in the molecule And polythiols formed by esterification with thioglycolic acid, β-mercaptopropionic acid, or β-mercaptobutanoic acid.
When the component (C) is contained in the photocurable resin composition, the content thereof is preferably 5 to 70% by mass, more preferably 10 to 50% by mass with respect to the photocurable resin composition.
（（Ｄ）添加剤）
本発明の光硬化性樹脂組成物は、さらに各種添加剤を含有していてもよい。
添加剤としては、例えば光増感剤、無機充填材、増粘剤、紫外線吸収剤、酸化防止剤（老化防止剤）や、Ｎ，Ｎ′－ジフェニルカルボジイミド、Ｎ，Ｎ′－エチルカルボジイミド等のカルボジイミド化合物等が挙げられる。
－光増感剤－
光増感剤としては、例えば、脂肪族アミン、芳香族アミン等のアミン化合物；ｏ－トリルチオ尿素等の尿素類；ナトリウムジエチルジチオホスフェート、ｓ－ベンジルイソチウロニウム－ｐ－トルエンスルフォネート等のイオウ化合物；Ｎ，Ｎ－ジ置換－ｐ－アミノベンゾニトリル化合物等のニトリル類；トリ－ｎ－ブチルホスフィン等のリン化合物；Ｎ－ニトロソヒドロキシルアミン誘導体等のその他の窒素化合物等を挙げることができる。 ((D) Additive)
The photocurable resin composition of the present invention may further contain various additives.
Examples of additives include photosensitizers, inorganic fillers, thickeners, ultraviolet absorbers, antioxidants (anti-aging agents), N, N′-diphenylcarbodiimide, N, N′-ethylcarbodiimide, and the like. Examples thereof include carbodiimide compounds.
-Photosensitizer-
Examples of photosensitizers include amine compounds such as aliphatic amines and aromatic amines; ureas such as o-tolylthiourea; sodium diethyldithiophosphate, s-benzylisothiouronium-p-toluenesulfonate, and the like. Sulfur compounds; Nitriles such as N, N-disubstituted-p-aminobenzonitrile compounds; Phosphorus compounds such as tri-n-butylphosphine; Other nitrogen compounds such as N-nitrosohydroxylamine derivatives .
本発明の光硬化性樹脂組成物は、さらに各種添加剤を含有していてもよい。
添加剤としては、例えば光増感剤、無機充填材、増粘剤、紫外線吸収剤、酸化防止剤（老化防止剤）や、Ｎ，Ｎ′－ジフェニルカルボジイミド、Ｎ，Ｎ′－エチルカルボジイミド等のカルボジイミド化合物等が挙げられる。
－光増感剤－
光増感剤としては、例えば、脂肪族アミン、芳香族アミン等のアミン化合物；ｏ－トリルチオ尿素等の尿素類；ナトリウムジエチルジチオホスフェート、ｓ－ベンジルイソチウロニウム－ｐ－トルエンスルフォネート等のイオウ化合物；Ｎ，Ｎ－ジ置換－ｐ－アミノベンゾニトリル化合物等のニトリル類；トリ－ｎ－ブチルホスフィン等のリン化合物；Ｎ－ニトロソヒドロキシルアミン誘導体等のその他の窒素化合物等を挙げることができる。 ((D) Additive)
The photocurable resin composition of the present invention may further contain various additives.
Examples of additives include photosensitizers, inorganic fillers, thickeners, ultraviolet absorbers, antioxidants (anti-aging agents), N, N′-diphenylcarbodiimide, N, N′-ethylcarbodiimide, and the like. Examples thereof include carbodiimide compounds.
-Photosensitizer-
Examples of photosensitizers include amine compounds such as aliphatic amines and aromatic amines; ureas such as o-tolylthiourea; sodium diethyldithiophosphate, s-benzylisothiouronium-p-toluenesulfonate, and the like. Sulfur compounds; Nitriles such as N, N-disubstituted-p-aminobenzonitrile compounds; Phosphorus compounds such as tri-n-butylphosphine; Other nitrogen compounds such as N-nitrosohydroxylamine derivatives .
－増粘剤－
光硬化性樹脂組成物に増粘剤を含有させることにより、増粘性や揺変性（チクソトロピー）が付与され、成形性を向上させることができる。該増粘剤としては、無機充填剤及び有機増粘剤が挙げられる。
無機充填剤としては、湿式シリカや乾式シリカの表面処理微粉シリカや、有機化ベントナイト等の天然鉱物系のものが挙げられる。より具体的には、乾式法により微粉化したシリカ微粉末［例えば、「アエロジル３００」（日本アエロジル株式会社製）等］、このシリカ微粉末をトリメチルジシラザンで変性した微粉末［例えば、「アエロジルＲＸ３００」（日本アエロジル株式会社製）等］及び上記シリカ微粉末をポリジメチルシロキサンで変性した微粉末［例えば、「アエロジルＲＹ３００」（日本アエロジル株式会社製）等］等が挙げられる。無機充填剤の平均粒径は、増粘性及び透明性の観点から、５～５０μｍが好ましく、５～１２μｍがより好ましい。
有機増粘剤としては、アマイドワックス、水添ひまし油系又はこれらの混合物等が挙げられる。より具体的には、ひまし油（主成分がリシノール酸の不乾性油）の水添品である水添ひまし油［例えば、「ＡＤＶＩＴＲＯＬ １００」（ズードケミー触媒株式会社製）、「ディスパロン（登録商標）３０５」（楠本化成株式会社製）等］及びアンモニアの水素をアシル基で置換した化合物である高級アマイドワックス［例えば、「ディスパロン（登録商標）６５００」（楠本化成株式会社製）等］等が挙げられる。 -Thickener-
By adding a thickener to the photocurable resin composition, thickening and thixotropic properties are imparted, and moldability can be improved. Examples of the thickener include inorganic fillers and organic thickeners.
Examples of the inorganic filler include surface-treated fine silica of wet silica and dry silica, and natural minerals such as organic bentonite. More specifically, silica fine powder pulverized by a dry method [for example, “Aerosil 300” (manufactured by Nippon Aerosil Co., Ltd.)], fine powder obtained by modifying this silica fine powder with trimethyldisilazane [for example, “Aerosil” RX300 "(manufactured by Nippon Aerosil Co., Ltd.) and the like] and fine powder obtained by modifying the silica fine powder with polydimethylsiloxane [for example," Aerosil RY300 "(manufactured by Nippon Aerosil Co., Ltd.)] and the like. The average particle diameter of the inorganic filler is preferably 5 to 50 μm, more preferably 5 to 12 μm, from the viewpoints of thickening and transparency.
Examples of the organic thickener include amide wax, hydrogenated castor oil, or a mixture thereof. More specifically, hydrogenated castor oil which is a hydrogenated product of castor oil (non-drying oil whose main component is ricinoleic acid) [for example, “ADVITOLOL 100” (manufactured by Zudchemy Catalyst Co., Ltd.), “Disparon (registered trademark) 305” (Made by Enomoto Kasei Co., Ltd.) and the like, and higher amide waxes which are compounds obtained by substituting hydrogen of ammonia with an acyl group [for example, “Disparon (registered trademark) 6500” (made by Enomoto Kasei Co., Ltd.)] and the like.
光硬化性樹脂組成物に増粘剤を含有させることにより、増粘性や揺変性（チクソトロピー）が付与され、成形性を向上させることができる。該増粘剤としては、無機充填剤及び有機増粘剤が挙げられる。
無機充填剤としては、湿式シリカや乾式シリカの表面処理微粉シリカや、有機化ベントナイト等の天然鉱物系のものが挙げられる。より具体的には、乾式法により微粉化したシリカ微粉末［例えば、「アエロジル３００」（日本アエロジル株式会社製）等］、このシリカ微粉末をトリメチルジシラザンで変性した微粉末［例えば、「アエロジルＲＸ３００」（日本アエロジル株式会社製）等］及び上記シリカ微粉末をポリジメチルシロキサンで変性した微粉末［例えば、「アエロジルＲＹ３００」（日本アエロジル株式会社製）等］等が挙げられる。無機充填剤の平均粒径は、増粘性及び透明性の観点から、５～５０μｍが好ましく、５～１２μｍがより好ましい。
有機増粘剤としては、アマイドワックス、水添ひまし油系又はこれらの混合物等が挙げられる。より具体的には、ひまし油（主成分がリシノール酸の不乾性油）の水添品である水添ひまし油［例えば、「ＡＤＶＩＴＲＯＬ １００」（ズードケミー触媒株式会社製）、「ディスパロン（登録商標）３０５」（楠本化成株式会社製）等］及びアンモニアの水素をアシル基で置換した化合物である高級アマイドワックス［例えば、「ディスパロン（登録商標）６５００」（楠本化成株式会社製）等］等が挙げられる。 -Thickener-
By adding a thickener to the photocurable resin composition, thickening and thixotropic properties are imparted, and moldability can be improved. Examples of the thickener include inorganic fillers and organic thickeners.
Examples of the inorganic filler include surface-treated fine silica of wet silica and dry silica, and natural minerals such as organic bentonite. More specifically, silica fine powder pulverized by a dry method [for example, “Aerosil 300” (manufactured by Nippon Aerosil Co., Ltd.)], fine powder obtained by modifying this silica fine powder with trimethyldisilazane [for example, “Aerosil” RX300 "(manufactured by Nippon Aerosil Co., Ltd.) and the like] and fine powder obtained by modifying the silica fine powder with polydimethylsiloxane [for example," Aerosil RY300 "(manufactured by Nippon Aerosil Co., Ltd.)] and the like. The average particle diameter of the inorganic filler is preferably 5 to 50 μm, more preferably 5 to 12 μm, from the viewpoints of thickening and transparency.
Examples of the organic thickener include amide wax, hydrogenated castor oil, or a mixture thereof. More specifically, hydrogenated castor oil which is a hydrogenated product of castor oil (non-drying oil whose main component is ricinoleic acid) [for example, “ADVITOLOL 100” (manufactured by Zudchemy Catalyst Co., Ltd.), “Disparon (registered trademark) 305” (Made by Enomoto Kasei Co., Ltd.) and the like, and higher amide waxes which are compounds obtained by substituting hydrogen of ammonia with an acyl group [for example, “Disparon (registered trademark) 6500” (made by Enomoto Kasei Co., Ltd.)] and the like.
－紫外線吸収剤－
紫外線吸収剤としては、例えば、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、ベンゾエート系化合物、トリアジン系化合物、ヒドロキシルアミン系化合物等が挙げられる。
－酸化防止剤－
酸化防止剤としては、例えばフェノール系酸化防止剤、イオウ系酸化防止剤、リン系酸化防止剤等が挙げられる。
フェノール系酸化防止剤としては、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、ブチル化ヒドロキシアニソール、２，６－ジ－ｔ－プチル－４－エチルフェノール、ステアリル－β－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、２，２'－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、２，２'－メチレンビス（４－エチル－６－ｔ－ブチルフェノール）、４，４'－チオビス（３－メチル－６－ｔ－ブチルフェノール）、４，４'－ブチリデンビス（３－メチル－６－ｔ－ブチルフェノール）、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニルブタン、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、テトラキス－〔メチレン－３－（３'，５'－ジ－ｔ－ブチル－４'－ヒドロキシフェニル）プロピオネート〕メタン、ビス〔３，３'－ビス－（４'－ヒドロキシ－３'－ｔ－ブチルフェニル）ブチリックアシッド〕グリコールエステル、１，３，５－トリス（３'，５'－ジ－ｔ－ブチル－４'－ヒドロキシベンジル）－Ｓ－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）トリオン、α－トコフェロール等が例示される。
イオウ系酸化防止剤としては、ジラウリル３，３'－チオジプロピオネート、ジミリスチル３，３'－チオジプロピオネート、ジステアリル３，３'－チオジプロピオネート等が例示され、またリン系酸化防止剤としては、トリフェニルホスファイト、ジフェニルイソデシルホスファイト、フェニルイソデシルホスファイト、トリス（ノニルフェニル）ホスファイト、トリス（２，４－ジ－ｔ－ブチルフェニル）ホスファイト、２，２'－メチレンビス（４，６－ジ－ｔ－ブチルフェニル）オクチルホスファイト等が例示される。
光硬化性樹脂組成物に（Ｄ）添加剤を含有させる場合、その合計含有量は、本発明の効果を失わない程度であれば特に制限はないが、（Ａ）成分１００質量部に対して、通常、好ましくは２０質量部以下、より好ましくは１０質量部以下である。 -UV absorber-
Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, benzoate compounds, triazine compounds, hydroxylamine compounds, and the like.
-Antioxidant-
Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.
Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4- Hydroxy-5-tert-butylphenylbutane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis -[Methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4′-hydroxy-3′-t-butyl) Phenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H , 5H) trione, α-tocopherol and the like.
Examples of sulfur-based antioxidants include dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, and phosphorus-based oxidation Examples of the inhibitor include triphenyl phosphite, diphenylisodecyl phosphite, phenylisodecyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, Examples include -methylenebis (4,6-di-t-butylphenyl) octyl phosphite.
When the (D) additive is contained in the photocurable resin composition, the total content is not particularly limited as long as the effect of the present invention is not lost, but with respect to 100 parts by mass of component (A). Usually, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.
紫外線吸収剤としては、例えば、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、ベンゾエート系化合物、トリアジン系化合物、ヒドロキシルアミン系化合物等が挙げられる。
－酸化防止剤－
酸化防止剤としては、例えばフェノール系酸化防止剤、イオウ系酸化防止剤、リン系酸化防止剤等が挙げられる。
フェノール系酸化防止剤としては、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、ブチル化ヒドロキシアニソール、２，６－ジ－ｔ－プチル－４－エチルフェノール、ステアリル－β－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、２，２'－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、２，２'－メチレンビス（４－エチル－６－ｔ－ブチルフェノール）、４，４'－チオビス（３－メチル－６－ｔ－ブチルフェノール）、４，４'－ブチリデンビス（３－メチル－６－ｔ－ブチルフェノール）、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニルブタン、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、テトラキス－〔メチレン－３－（３'，５'－ジ－ｔ－ブチル－４'－ヒドロキシフェニル）プロピオネート〕メタン、ビス〔３，３'－ビス－（４'－ヒドロキシ－３'－ｔ－ブチルフェニル）ブチリックアシッド〕グリコールエステル、１，３，５－トリス（３'，５'－ジ－ｔ－ブチル－４'－ヒドロキシベンジル）－Ｓ－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）トリオン、α－トコフェロール等が例示される。
イオウ系酸化防止剤としては、ジラウリル３，３'－チオジプロピオネート、ジミリスチル３，３'－チオジプロピオネート、ジステアリル３，３'－チオジプロピオネート等が例示され、またリン系酸化防止剤としては、トリフェニルホスファイト、ジフェニルイソデシルホスファイト、フェニルイソデシルホスファイト、トリス（ノニルフェニル）ホスファイト、トリス（２，４－ジ－ｔ－ブチルフェニル）ホスファイト、２，２'－メチレンビス（４，６－ジ－ｔ－ブチルフェニル）オクチルホスファイト等が例示される。
光硬化性樹脂組成物に（Ｄ）添加剤を含有させる場合、その合計含有量は、本発明の効果を失わない程度であれば特に制限はないが、（Ａ）成分１００質量部に対して、通常、好ましくは２０質量部以下、より好ましくは１０質量部以下である。 -UV absorber-
Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, benzoate compounds, triazine compounds, hydroxylamine compounds, and the like.
-Antioxidant-
Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.
Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4- Hydroxy-5-tert-butylphenylbutane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis -[Methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4′-hydroxy-3′-t-butyl) Phenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H , 5H) trione, α-tocopherol and the like.
Examples of sulfur-based antioxidants include dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, and phosphorus-based oxidation Examples of the inhibitor include triphenyl phosphite, diphenylisodecyl phosphite, phenylisodecyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, Examples include -methylenebis (4,6-di-t-butylphenyl) octyl phosphite.
When the (D) additive is contained in the photocurable resin composition, the total content is not particularly limited as long as the effect of the present invention is not lost, but with respect to 100 parts by mass of component (A). Usually, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.
前記（Ａ）成分及び（Ｂ）成分、並びに必要に応じて（Ｃ）成分や（Ｄ）成分等を混合することにより、本発明の光硬化性樹脂組成物を得ることができる。本発明の光硬化性樹脂組成物は、耐熱性及び光透過性に優れるため、特に発光素子封止材として有用である。なお、発光素子としては、有機エレクトロルミネッセンス素子及び無機エレクトロルミネッセンス素子に代表される発光ダイオード（ＬＥＤ）、通信や光ディスクの光源として使用されるレーザーダイオード（ＬＤ）が挙げられる。
The photocurable resin composition of the present invention can be obtained by mixing the component (A) and the component (B) and, if necessary, the component (C) and the component (D). Since the photocurable resin composition of the present invention is excellent in heat resistance and light transmittance, it is particularly useful as a light emitting device sealing material. In addition, as a light emitting element, the light emitting diode (LED) represented by the organic electroluminescent element and the inorganic electroluminescent element, and the laser diode (LD) used as a light source of communication and an optical disk are mentioned.
［発光素子封止材］
本発明の光硬化性樹脂組成物を用いることにより、発光素子封止材を製造することができる。具体的には、例えばプラネタリーミキサー等の混合機にてよく混合して得られた光硬化性樹脂組成物は、発光素子の封止すべき箇所へ塗布され、活性エネルギー線照射により硬化され、発光素子封止材となる。該活性エネルギー線としては、粒子線、電磁波及びこれらの組み合わせが挙げられる。粒子線としては、電子線（ＥＢ）及びα線が挙げられ、電磁波としては、紫外線（ＵＶ）、可視光線、赤外線、γ線及びＸ線等が挙げられる。これらの中でも、活性エネルギー線としては、紫外線を使用することが好ましい。紫外線源としては、キセノンランプ、低圧水銀ランプ、高圧水銀ランプ、メタルハライドランプ、マイクロ波方式エキシマランプ等を挙げることができる。
活性エネルギー線は、窒素ガスや炭酸ガス等の不活性ガス雰囲気又は酸素濃度を低下させた雰囲気下にて照射することが好ましいが、通常の空気雰囲気でも十分に硬化させることができる。照射温度は、通常、好ましくは１０～２００℃であり、照射時間は、通常、好ましくは１０秒～６０分である。積算光量は、通常、好ましくは１，０００～２０，０００ｍＪ／ｃｍ2である。 [Light emitting element sealing material]
By using the photocurable resin composition of the present invention, a light emitting device sealing material can be produced. Specifically, for example, a photocurable resin composition obtained by mixing well in a mixer such as a planetary mixer is applied to a portion to be sealed of the light emitting element, cured by irradiation with active energy rays, It becomes a light emitting element sealing material. Examples of the active energy rays include particle rays, electromagnetic waves, and combinations thereof. Examples of the particle beam include an electron beam (EB) and an α ray, and examples of the electromagnetic wave include an ultraviolet ray (UV), a visible ray, an infrared ray, a γ ray and an X ray. Among these, it is preferable to use ultraviolet rays as active energy rays. Examples of the ultraviolet light source include a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a microwave excimer lamp.
The active energy ray is preferably irradiated in an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere in which the oxygen concentration is lowered, but can be sufficiently cured even in a normal air atmosphere. The irradiation temperature is usually preferably 10 to 200 ° C., and the irradiation time is usually preferably 10 seconds to 60 minutes. The integrated light quantity is usually preferably 1,000 to 20,000 mJ / cm 2 .
本発明の光硬化性樹脂組成物を用いることにより、発光素子封止材を製造することができる。具体的には、例えばプラネタリーミキサー等の混合機にてよく混合して得られた光硬化性樹脂組成物は、発光素子の封止すべき箇所へ塗布され、活性エネルギー線照射により硬化され、発光素子封止材となる。該活性エネルギー線としては、粒子線、電磁波及びこれらの組み合わせが挙げられる。粒子線としては、電子線（ＥＢ）及びα線が挙げられ、電磁波としては、紫外線（ＵＶ）、可視光線、赤外線、γ線及びＸ線等が挙げられる。これらの中でも、活性エネルギー線としては、紫外線を使用することが好ましい。紫外線源としては、キセノンランプ、低圧水銀ランプ、高圧水銀ランプ、メタルハライドランプ、マイクロ波方式エキシマランプ等を挙げることができる。
活性エネルギー線は、窒素ガスや炭酸ガス等の不活性ガス雰囲気又は酸素濃度を低下させた雰囲気下にて照射することが好ましいが、通常の空気雰囲気でも十分に硬化させることができる。照射温度は、通常、好ましくは１０～２００℃であり、照射時間は、通常、好ましくは１０秒～６０分である。積算光量は、通常、好ましくは１，０００～２０，０００ｍＪ／ｃｍ2である。 [Light emitting element sealing material]
By using the photocurable resin composition of the present invention, a light emitting device sealing material can be produced. Specifically, for example, a photocurable resin composition obtained by mixing well in a mixer such as a planetary mixer is applied to a portion to be sealed of the light emitting element, cured by irradiation with active energy rays, It becomes a light emitting element sealing material. Examples of the active energy rays include particle rays, electromagnetic waves, and combinations thereof. Examples of the particle beam include an electron beam (EB) and an α ray, and examples of the electromagnetic wave include an ultraviolet ray (UV), a visible ray, an infrared ray, a γ ray and an X ray. Among these, it is preferable to use ultraviolet rays as active energy rays. Examples of the ultraviolet light source include a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a microwave excimer lamp.
The active energy ray is preferably irradiated in an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere in which the oxygen concentration is lowered, but can be sufficiently cured even in a normal air atmosphere. The irradiation temperature is usually preferably 10 to 200 ° C., and the irradiation time is usually preferably 10 seconds to 60 minutes. The integrated light quantity is usually preferably 1,000 to 20,000 mJ / cm 2 .
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
＜製造例１＞末端変性水添スチレンブタジエンゴムの製造
アルゴン置換した内容積７Ｌの反応器に、脱水精製したシクロヘキサン１．９０ｋｇ、２２．９質量％の１，３－ブタジエンのヘキサン溶液２ｋｇ、２０．０質量％のスチレンのシクロヘキサン溶液０．５７３ｋｇ、１．６ｍｏｌ／Ｌの２，２－ジ（テトラヒドロフリル）プロパンのヘキサン溶液１３０．４ｍｌを添加した後、０．５ｍｏｌ／Ｌのジリチウム重合開始剤１０８．０ｍｌを添加して重合を開始させた。混合液を５０℃に昇温し、１．５時間重合を行なった後、１ｍｏｌ／Ｌのエチレンオキシドのシクロヘキサン溶液１０８．０ｍｌを添加し、さらに２時間撹拌した後、５０ｍｌのイソプロピルアルコールを添加した。
得られた共重合体のヘキサン溶液をイソプロピルアルコール中に沈殿させ、十分に乾燥させて、分子末端に水酸基を有するスチレンブタジエンゴム（スチレン含有量：２０質量％、重量平均分子量１８，０００、分子量分布１．１５）を得た。 <Production Example 1> Production of terminal-modified hydrogenated styrene-butadiene rubber Into a reactor having an internal volume of 7 L purged with argon, 1.90 kg of dehydrated and purified cyclohexane, 2 kg of hexane solution of 22.9% by mass of 1,3-butadiene, 20 kg After adding 0.573 kg of a 0.0 mass% styrene cyclohexane solution and 130.4 ml of a 1.6 mol / L hexane solution of 2,2-di (tetrahydrofuryl) propane, a 0.5 mol / L dilithium polymerization initiator was added. 108.0 ml was added to initiate the polymerization. The mixture was heated to 50 ° C., polymerized for 1.5 hours, 108.0 ml of a 1 mol / L ethylene oxide cyclohexane solution was added, and the mixture was further stirred for 2 hours, and then 50 ml of isopropyl alcohol was added.
A hexane solution of the obtained copolymer is precipitated in isopropyl alcohol and sufficiently dried to give a styrene butadiene rubber having a hydroxyl group at the molecular end (styrene content: 20% by mass, weight average molecular weight 18,000, molecular weight distribution). 1.15) was obtained.
アルゴン置換した内容積７Ｌの反応器に、脱水精製したシクロヘキサン１．９０ｋｇ、２２．９質量％の１，３－ブタジエンのヘキサン溶液２ｋｇ、２０．０質量％のスチレンのシクロヘキサン溶液０．５７３ｋｇ、１．６ｍｏｌ／Ｌの２，２－ジ（テトラヒドロフリル）プロパンのヘキサン溶液１３０．４ｍｌを添加した後、０．５ｍｏｌ／Ｌのジリチウム重合開始剤１０８．０ｍｌを添加して重合を開始させた。混合液を５０℃に昇温し、１．５時間重合を行なった後、１ｍｏｌ／Ｌのエチレンオキシドのシクロヘキサン溶液１０８．０ｍｌを添加し、さらに２時間撹拌した後、５０ｍｌのイソプロピルアルコールを添加した。
得られた共重合体のヘキサン溶液をイソプロピルアルコール中に沈殿させ、十分に乾燥させて、分子末端に水酸基を有するスチレンブタジエンゴム（スチレン含有量：２０質量％、重量平均分子量１８，０００、分子量分布１．１５）を得た。 <Production Example 1> Production of terminal-modified hydrogenated styrene-butadiene rubber Into a reactor having an internal volume of 7 L purged with argon, 1.90 kg of dehydrated and purified cyclohexane, 2 kg of hexane solution of 22.9% by mass of 1,3-butadiene, 20 kg After adding 0.573 kg of a 0.0 mass% styrene cyclohexane solution and 130.4 ml of a 1.6 mol / L hexane solution of 2,2-di (tetrahydrofuryl) propane, a 0.5 mol / L dilithium polymerization initiator was added. 108.0 ml was added to initiate the polymerization. The mixture was heated to 50 ° C., polymerized for 1.5 hours, 108.0 ml of a 1 mol / L ethylene oxide cyclohexane solution was added, and the mixture was further stirred for 2 hours, and then 50 ml of isopropyl alcohol was added.
A hexane solution of the obtained copolymer is precipitated in isopropyl alcohol and sufficiently dried to give a styrene butadiene rubber having a hydroxyl group at the molecular end (styrene content: 20% by mass, weight average molecular weight 18,000, molecular weight distribution). 1.15) was obtained.
（水素添加処理）
上記で得られた分子末端に水酸基を有するスチレンブタジエンゴム１２０ｇを、十分に脱水精製したヘキサン１Ｌに溶解した後、予め別の容器で調整したナフテン酸ニッケル、トリエチルアルミニウム及びブタジエン［それぞれ１：３：３（モル比）］の触媒液を、前記スチレンブタジエンゴムのブタジエン由来の構成単位１０００ｍｏｌに対してニッケル１ｍｏｌになるように仕込んだ。密閉反応容器に水素を２．７５８ＭＰａ（４００ｐｓｉ）で加圧添加し、１１０℃にて４時間、水素添加反応を行なった。
その後、３ｍｏｌ／ｍ3の塩酸で触媒残渣を抽出分離し、さらに遠心分離をして触媒残渣を沈降分離した。そして、分子末端に水酸基を有する水添スチレンブタジエンゴムをイソプロピルアルコール中に沈殿させ、さらに十分に乾燥させて、分子末端に水酸基を有する水添スチレンブタジエンゴム（スチレン含有量２０質量％、重量平均分子量１６，５００、水素添加率：９８％、分子量分布１．１）を得た。
（分子末端の変性処理）
こうして得られた分子末端に水酸基を有する水添スチレンブタジエンゴムをシクロヘキサンに溶解し、４０℃にて攪拌しながら２－アクリロイルオキシエチルイソシアネート（「カレンズ（登録商標）ＡＯＩ」、昭和電工株式会社製）をゆっくり滴下し、さらに４時間攪拌を行なった後、イソプロピルアルコール中に結晶を沈殿させ、末端変性水添スチレンブタジエンゴムを得た。 (Hydrogenation treatment)
120 g of styrene butadiene rubber having a hydroxyl group at the molecular end obtained above was dissolved in 1 L of sufficiently dehydrated and purified hexane, and then nickel naphthenate, triethylaluminum and butadiene prepared in separate containers in advance [1: 3: 3 (molar ratio)] was charged to 1 mol of nickel with respect to 1000 mol of the butadiene-derived structural unit of the styrene-butadiene rubber. Hydrogen was added under pressure at 2.758 MPa (400 psi) to the sealed reaction vessel, and a hydrogenation reaction was performed at 110 ° C. for 4 hours.
Thereafter, the catalyst residue was extracted and separated with 3 mol / m 3 hydrochloric acid, and further centrifuged to separate the catalyst residue by sedimentation. Then, a hydrogenated styrene butadiene rubber having a hydroxyl group at the molecular end is precipitated in isopropyl alcohol and further sufficiently dried to obtain a hydrogenated styrene butadiene rubber having a hydroxyl group at the molecular end (styrene content 20 mass%, weight average molecular weight). 16,500, hydrogenation rate: 98%, molecular weight distribution 1.1) was obtained.
(Modification of molecular ends)
The thus obtained hydrogenated styrene butadiene rubber having a hydroxyl group at the molecular end is dissolved in cyclohexane and stirred at 40 ° C., 2-acryloyloxyethyl isocyanate (“Karenz (registered trademark) AOI”, manufactured by Showa Denko KK). Was slowly added dropwise, and the mixture was further stirred for 4 hours, and then crystals were precipitated in isopropyl alcohol to obtain a terminal-modified hydrogenated styrene butadiene rubber.
上記で得られた分子末端に水酸基を有するスチレンブタジエンゴム１２０ｇを、十分に脱水精製したヘキサン１Ｌに溶解した後、予め別の容器で調整したナフテン酸ニッケル、トリエチルアルミニウム及びブタジエン［それぞれ１：３：３（モル比）］の触媒液を、前記スチレンブタジエンゴムのブタジエン由来の構成単位１０００ｍｏｌに対してニッケル１ｍｏｌになるように仕込んだ。密閉反応容器に水素を２．７５８ＭＰａ（４００ｐｓｉ）で加圧添加し、１１０℃にて４時間、水素添加反応を行なった。
その後、３ｍｏｌ／ｍ3の塩酸で触媒残渣を抽出分離し、さらに遠心分離をして触媒残渣を沈降分離した。そして、分子末端に水酸基を有する水添スチレンブタジエンゴムをイソプロピルアルコール中に沈殿させ、さらに十分に乾燥させて、分子末端に水酸基を有する水添スチレンブタジエンゴム（スチレン含有量２０質量％、重量平均分子量１６，５００、水素添加率：９８％、分子量分布１．１）を得た。
（分子末端の変性処理）
こうして得られた分子末端に水酸基を有する水添スチレンブタジエンゴムをシクロヘキサンに溶解し、４０℃にて攪拌しながら２－アクリロイルオキシエチルイソシアネート（「カレンズ（登録商標）ＡＯＩ」、昭和電工株式会社製）をゆっくり滴下し、さらに４時間攪拌を行なった後、イソプロピルアルコール中に結晶を沈殿させ、末端変性水添スチレンブタジエンゴムを得た。 (Hydrogenation treatment)
120 g of styrene butadiene rubber having a hydroxyl group at the molecular end obtained above was dissolved in 1 L of sufficiently dehydrated and purified hexane, and then nickel naphthenate, triethylaluminum and butadiene prepared in separate containers in advance [1: 3: 3 (molar ratio)] was charged to 1 mol of nickel with respect to 1000 mol of the butadiene-derived structural unit of the styrene-butadiene rubber. Hydrogen was added under pressure at 2.758 MPa (400 psi) to the sealed reaction vessel, and a hydrogenation reaction was performed at 110 ° C. for 4 hours.
Thereafter, the catalyst residue was extracted and separated with 3 mol / m 3 hydrochloric acid, and further centrifuged to separate the catalyst residue by sedimentation. Then, a hydrogenated styrene butadiene rubber having a hydroxyl group at the molecular end is precipitated in isopropyl alcohol and further sufficiently dried to obtain a hydrogenated styrene butadiene rubber having a hydroxyl group at the molecular end (styrene content 20 mass%, weight average molecular weight). 16,500, hydrogenation rate: 98%, molecular weight distribution 1.1) was obtained.
(Modification of molecular ends)
The thus obtained hydrogenated styrene butadiene rubber having a hydroxyl group at the molecular end is dissolved in cyclohexane and stirred at 40 ° C., 2-acryloyloxyethyl isocyanate (“Karenz (registered trademark) AOI”, manufactured by Showa Denko KK). Was slowly added dropwise, and the mixture was further stirred for 4 hours, and then crystals were precipitated in isopropyl alcohol to obtain a terminal-modified hydrogenated styrene butadiene rubber.
＜実施例１～４、比較例１～６＞
表１、表２に示した配合量（単位：質量部）で各成分をプラネタリーミキサーにて混合し、光硬化性樹脂組成物を得た。得られた光硬化性樹脂組成物を、硬化後の厚さが１ｍｍ又は２ｍｍとなるように成膜し、活性エネルギー線を照射することにより、試験片としての硬化物を得た。
なお、活性エネルギー線の光源としては、メタルハライドランプ（装置名「ＳＥ－１５００Ｍ」、センエンジニアリング株式会社製）を使用し、紫外線照射機（装置名「ＵＶ１５０１ＢＡ－ＬＴ」、センエンジニアリング株式会社製）により、空気雰囲気下で放射照度１５０ｍＷ／ｃｍ2（波長：３２０～３９０ｎｍ）にて６０秒間照射を行った。
得られた試験片（厚さ１ｍｍ又は２ｍｍ）について、以下の方法により光透過率を測定した。結果を表１に示す。 <Examples 1 to 4, Comparative Examples 1 to 6>
Each component was mixed with the planetary mixer by the compounding quantity (unit: mass part) shown in Table 1 and Table 2, and the photocurable resin composition was obtained. The obtained photocurable resin composition was formed into a film having a thickness of 1 mm or 2 mm after curing, and irradiated with active energy rays to obtain a cured product as a test piece.
As a light source for active energy rays, a metal halide lamp (device name “SE-1500M”, manufactured by Sen Engineering Co., Ltd.) was used, and an ultraviolet irradiation device (device name “UV1501BA-LT”, manufactured by Sen Engineering Co., Ltd.) was used. Irradiation was performed in an air atmosphere at an irradiance of 150 mW / cm 2 (wavelength: 320 to 390 nm) for 60 seconds.
About the obtained test piece (1 mm or 2 mm in thickness), the light transmittance was measured by the following method. The results are shown in Table 1.
表１、表２に示した配合量（単位：質量部）で各成分をプラネタリーミキサーにて混合し、光硬化性樹脂組成物を得た。得られた光硬化性樹脂組成物を、硬化後の厚さが１ｍｍ又は２ｍｍとなるように成膜し、活性エネルギー線を照射することにより、試験片としての硬化物を得た。
なお、活性エネルギー線の光源としては、メタルハライドランプ（装置名「ＳＥ－１５００Ｍ」、センエンジニアリング株式会社製）を使用し、紫外線照射機（装置名「ＵＶ１５０１ＢＡ－ＬＴ」、センエンジニアリング株式会社製）により、空気雰囲気下で放射照度１５０ｍＷ／ｃｍ2（波長：３２０～３９０ｎｍ）にて６０秒間照射を行った。
得られた試験片（厚さ１ｍｍ又は２ｍｍ）について、以下の方法により光透過率を測定した。結果を表１に示す。 <Examples 1 to 4, Comparative Examples 1 to 6>
Each component was mixed with the planetary mixer by the compounding quantity (unit: mass part) shown in Table 1 and Table 2, and the photocurable resin composition was obtained. The obtained photocurable resin composition was formed into a film having a thickness of 1 mm or 2 mm after curing, and irradiated with active energy rays to obtain a cured product as a test piece.
As a light source for active energy rays, a metal halide lamp (device name “SE-1500M”, manufactured by Sen Engineering Co., Ltd.) was used, and an ultraviolet irradiation device (device name “UV1501BA-LT”, manufactured by Sen Engineering Co., Ltd.) was used. Irradiation was performed in an air atmosphere at an irradiance of 150 mW / cm 2 (wavelength: 320 to 390 nm) for 60 seconds.
About the obtained test piece (1 mm or 2 mm in thickness), the light transmittance was measured by the following method. The results are shown in Table 1.
（光透過率の測定）
紫外可視分光光度計［装置名「Ｖ－５５０」、日本分光株式会社製、積分球「ＩＳＶ－４７０」（日本分光株式会社製）］を用いて、波長４００ｎｍの光の透過率及び波長４５０ｎｍの光の透過率をそれぞれ測定した。
なお、特に厚さ２ｍｍの試験片において、波長４００ｎｍの光の透過率が８０％以上であると、発光素子封止材として有用であり、また、光透過率が高いほど好ましい。 (Measurement of light transmittance)
Using a UV-visible spectrophotometer [device name “V-550”, manufactured by JASCO Corporation, integrating sphere “ISV-470” (manufactured by JASCO Corporation)], the transmittance of light having a wavelength of 400 nm and the wavelength of 450 nm Each light transmittance was measured.
In particular, in a test piece having a thickness of 2 mm, the transmittance of light having a wavelength of 400 nm is 80% or more, which is useful as a light-emitting device sealing material, and the higher the light transmittance, the better.
紫外可視分光光度計［装置名「Ｖ－５５０」、日本分光株式会社製、積分球「ＩＳＶ－４７０」（日本分光株式会社製）］を用いて、波長４００ｎｍの光の透過率及び波長４５０ｎｍの光の透過率をそれぞれ測定した。
なお、特に厚さ２ｍｍの試験片において、波長４００ｎｍの光の透過率が８０％以上であると、発光素子封止材として有用であり、また、光透過率が高いほど好ましい。 (Measurement of light transmittance)
Using a UV-visible spectrophotometer [device name “V-550”, manufactured by JASCO Corporation, integrating sphere “ISV-470” (manufactured by JASCO Corporation)], the transmittance of light having a wavelength of 400 nm and the wavelength of 450 nm Each light transmittance was measured.
In particular, in a test piece having a thickness of 2 mm, the transmittance of light having a wavelength of 400 nm is 80% or more, which is useful as a light-emitting device sealing material, and the higher the light transmittance, the better.
表１より、本発明の光硬化性樹脂組成物から得られた硬化物は、比較例で得られた硬化物よりも光透過率が高く、また、厚さ２ｍｍの試験片を用いた場合でも光透過率が８０％を超えており、発光素子封止材として有用であることがわかる。
比較例６では、（Ｂ）成分の含有量を増加したところ、（Ｂ）成分が溶解しきっておらず、そのために光透過率が大幅に減少したものと考えられる。 From Table 1, the cured product obtained from the photocurable resin composition of the present invention has a higher light transmittance than the cured product obtained in the comparative example, and even when a test piece having a thickness of 2 mm is used. It can be seen that the light transmittance exceeds 80%, which is useful as a light emitting device sealing material.
In Comparative Example 6, when the content of the component (B) was increased, the component (B) was not completely dissolved, and it is considered that the light transmittance was greatly reduced.
比較例６では、（Ｂ）成分の含有量を増加したところ、（Ｂ）成分が溶解しきっておらず、そのために光透過率が大幅に減少したものと考えられる。 From Table 1, the cured product obtained from the photocurable resin composition of the present invention has a higher light transmittance than the cured product obtained in the comparative example, and even when a test piece having a thickness of 2 mm is used. It can be seen that the light transmittance exceeds 80%, which is useful as a light emitting device sealing material.
In Comparative Example 6, when the content of the component (B) was increased, the component (B) was not completely dissolved, and it is considered that the light transmittance was greatly reduced.
＜試験例１＞耐熱性の測定
実施例１で得た光硬化性樹脂組成物の硬化物（厚さ２ｍｍ）を、１２０℃に１００時間又は１０００時間保持した後の光透過率と、１５０℃に１００時間又は１０００時間保持した後の波長４００ｎｍの光の透過率を前記同様の方法で測定し、初期を１００としたときの相対値を求め、得られた硬化物の耐熱性を評価した。結果を表２に示す。
なお、１２０℃又は１５０℃に保持したときの光透過率の減少幅が小さいと、耐熱性に優れることを示す。 <Test Example 1> Measurement of heat resistance Light transmittance after holding the cured product (thickness 2 mm) of the photocurable resin composition obtained in Example 1 at 120 ° C for 100 hours or 1000 hours, and 150 ° C. The transmittance of light having a wavelength of 400 nm after being held for 100 hours or 1000 hours was measured by the same method as described above, and the relative value when the initial value was taken as 100 was determined, and the heat resistance of the obtained cured product was evaluated. The results are shown in Table 2.
In addition, it shows that it is excellent in heat resistance, when the reduction | decrease width of the light transmittance when hold | maintaining at 120 degreeC or 150 degreeC is small.
実施例１で得た光硬化性樹脂組成物の硬化物（厚さ２ｍｍ）を、１２０℃に１００時間又は１０００時間保持した後の光透過率と、１５０℃に１００時間又は１０００時間保持した後の波長４００ｎｍの光の透過率を前記同様の方法で測定し、初期を１００としたときの相対値を求め、得られた硬化物の耐熱性を評価した。結果を表２に示す。
なお、１２０℃又は１５０℃に保持したときの光透過率の減少幅が小さいと、耐熱性に優れることを示す。 <Test Example 1> Measurement of heat resistance Light transmittance after holding the cured product (thickness 2 mm) of the photocurable resin composition obtained in Example 1 at 120 ° C for 100 hours or 1000 hours, and 150 ° C. The transmittance of light having a wavelength of 400 nm after being held for 100 hours or 1000 hours was measured by the same method as described above, and the relative value when the initial value was taken as 100 was determined, and the heat resistance of the obtained cured product was evaluated. The results are shown in Table 2.
In addition, it shows that it is excellent in heat resistance, when the reduction | decrease width of the light transmittance when hold | maintaining at 120 degreeC or 150 degreeC is small.
＜比較試験例１＞耐熱性の測定
実施例１において、（Ａ）成分の末端変性水添スチレンブタジエンゴムの代わりに、ウレタンアクリレート（「ライトタックＰＵＡ－ＫＨ３２Ｍ」、共栄社化学株式会社製）を用いたこと以外は同様にして硬化物（厚さ２ｍｍ）を得、上記試験例１と同様にして、得られた硬化物の耐熱性を評価した。結果を表２に示す。 <Comparative Test Example 1> Measurement of heat resistance In Example 1, urethane acrylate ("Light Tack PUA-KH32M", manufactured by Kyoeisha Chemical Co., Ltd.) is used instead of the terminal-modified hydrogenated styrene butadiene rubber of component (A). A cured product (thickness 2 mm) was obtained in the same manner except that it was, and in the same manner as in Test Example 1, the heat resistance of the obtained cured product was evaluated. The results are shown in Table 2.
実施例１において、（Ａ）成分の末端変性水添スチレンブタジエンゴムの代わりに、ウレタンアクリレート（「ライトタックＰＵＡ－ＫＨ３２Ｍ」、共栄社化学株式会社製）を用いたこと以外は同様にして硬化物（厚さ２ｍｍ）を得、上記試験例１と同様にして、得られた硬化物の耐熱性を評価した。結果を表２に示す。 <Comparative Test Example 1> Measurement of heat resistance In Example 1, urethane acrylate ("Light Tack PUA-KH32M", manufactured by Kyoeisha Chemical Co., Ltd.) is used instead of the terminal-modified hydrogenated styrene butadiene rubber of component (A). A cured product (thickness 2 mm) was obtained in the same manner except that it was, and in the same manner as in Test Example 1, the heat resistance of the obtained cured product was evaluated. The results are shown in Table 2.
表２より、本発明の光硬化性樹脂組成物を硬化して得られる硬化物は耐熱性に優れており、発光素子封止材として有用であることがわかる。
From Table 2, it can be seen that the cured product obtained by curing the photocurable resin composition of the present invention has excellent heat resistance and is useful as a light emitting device sealing material.
本発明の光硬化性樹脂組成物は、耐熱性及び光透過性に優れるため、有機エレクトロルミネッセンス素子及び無機エレクトロルミネッセンス素子等の電子ディスプレイの封止材用途や、ＬＥＤが用いられる携帯電話、デジタルビデオカメラ、ＰＤＡ等の電子機器のバックライト、大型ディスプレイ、道路表示器等の表示部、及び一般照明等の発光素子封止材用途として利用可能である。
Since the photocurable resin composition of the present invention is excellent in heat resistance and light transmittance, it is used as a sealing material for electronic displays such as organic electroluminescent elements and inorganic electroluminescent elements, mobile phones using LEDs, and digital video. It can be used as a backlight for electronic devices such as cameras and PDAs, a display unit such as a large display, a road indicator, and a light emitting element sealing material for general lighting.
Claims (5)
- （Ａ）末端変性水添スチレンブタジエンゴム１００質量部及び（Ｂ）α－ヒドロキシアルキルフェノン系光重合開始剤及び／又はアシルホスフィンオキシド系光重合開始剤０．１～１３質量部を含有する、光硬化性樹脂組成物。 A light containing 100 parts by mass of (A) terminal-modified hydrogenated styrene-butadiene rubber and (B) 0.1-13 parts by mass of an α-hydroxyalkylphenone photopolymerization initiator and / or an acylphosphine oxide photopolymerization initiator. Curable resin composition.
- （Ａ）成分の末端変性水添スチレンブタジエンゴムが、分子の両末端に（メタ）アクリロイルオキシ基を有する水添スチレンブタジエンゴムである、請求項１に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the terminal-modified hydrogenated styrene butadiene rubber of component (A) is a hydrogenated styrene butadiene rubber having (meth) acryloyloxy groups at both ends of the molecule.
- さらに、（Ｃ）反応性希釈剤として、（メタ）アクリルモノマー及び／又はポリチオール化合物を含有する、請求項１又は２に記載の光硬化性樹脂組成物。 Furthermore, (C) The photocurable resin composition of Claim 1 or 2 which contains a (meth) acryl monomer and / or a polythiol compound as a reactive diluent.
- 発光素子封止材用である、請求項１～３のいずれかに記載の光硬化性樹脂組成物。 4. The photocurable resin composition according to claim 1, which is used for a light emitting device sealing material.
- 請求項１～３のいずれかに記載の光硬化性樹脂組成物を用いた発光素子封止材。 A light emitting device sealing material using the photocurable resin composition according to any one of claims 1 to 3.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/522,116 US20120296000A1 (en) | 2010-01-15 | 2011-01-14 | Photocurable resin composition and light-emitting element sealant |
| CN2011800060986A CN102712729A (en) | 2010-01-15 | 2011-01-14 | Photocurable resin composition and light-emitting element sealant |
| EP11732971.4A EP2524933B1 (en) | 2010-01-15 | 2011-01-14 | Photocurable resin composition and light-emitting element sealant |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010006747A JP5946985B2 (en) | 2010-01-15 | 2010-01-15 | Photocurable resin composition and light emitting device sealing material |
| JP2010-006747 | 2010-01-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2011087101A1 true WO2011087101A1 (en) | 2011-07-21 |
Family
ID=44304370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2011/050578 WO2011087101A1 (en) | 2010-01-15 | 2011-01-14 | Photocurable resin composition and light-emitting element sealant |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20120296000A1 (en) |
| EP (1) | EP2524933B1 (en) |
| JP (1) | JP5946985B2 (en) |
| CN (1) | CN102712729A (en) |
| WO (1) | WO2011087101A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997044363A1 (en) * | 1996-05-23 | 1997-11-27 | Omron Corporation | Photosensitive composition and white coating |
| JP2002156498A (en) * | 2000-11-20 | 2002-05-31 | Fuji Photo Film Co Ltd | Radiation image conversion panel |
| JP2005129520A (en) * | 2003-10-03 | 2005-05-19 | Jsr Corp | Transparent sealant for organic el element |
| JP2008195792A (en) * | 2007-02-09 | 2008-08-28 | Bridgestone Corp | Photocurable liquid resin composition |
| JP2008291127A (en) * | 2007-05-25 | 2008-12-04 | Bridgestone Corp | Photocurable composition and gasket for electronic component using the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01113417A (en) * | 1987-10-26 | 1989-05-02 | Matsushita Electric Works Ltd | Photocuarable resin composition |
| KR20060090692A (en) * | 2003-10-03 | 2006-08-14 | 제이에스알 가부시끼가이샤 | Transparent sealing material for organic el device |
-
2010
- 2010-01-15 JP JP2010006747A patent/JP5946985B2/en not_active Expired - Fee Related
-
2011
- 2011-01-14 EP EP11732971.4A patent/EP2524933B1/en not_active Not-in-force
- 2011-01-14 CN CN2011800060986A patent/CN102712729A/en active Pending
- 2011-01-14 WO PCT/JP2011/050578 patent/WO2011087101A1/en active Application Filing
- 2011-01-14 US US13/522,116 patent/US20120296000A1/en not_active Abandoned
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997044363A1 (en) * | 1996-05-23 | 1997-11-27 | Omron Corporation | Photosensitive composition and white coating |
| JP2002156498A (en) * | 2000-11-20 | 2002-05-31 | Fuji Photo Film Co Ltd | Radiation image conversion panel |
| JP2005129520A (en) * | 2003-10-03 | 2005-05-19 | Jsr Corp | Transparent sealant for organic el element |
| JP2008195792A (en) * | 2007-02-09 | 2008-08-28 | Bridgestone Corp | Photocurable liquid resin composition |
| JP2008291127A (en) * | 2007-05-25 | 2008-12-04 | Bridgestone Corp | Photocurable composition and gasket for electronic component using the same |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP2524933A4 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20120296000A1 (en) | 2012-11-22 |
| EP2524933A1 (en) | 2012-11-21 |
| CN102712729A (en) | 2012-10-03 |
| EP2524933A4 (en) | 2014-08-20 |
| EP2524933B1 (en) | 2016-09-07 |
| JP2011144276A (en) | 2011-07-28 |
| JP5946985B2 (en) | 2016-07-06 |
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